Cationic dyes

ABSTRACT

The present invention relates to novel cationic dye of formula (1)  
                 
 
     wherein  
     R 1  and R 7  are each independently of the other hydrogen, hydroxyl; unsubstituted or substituted C 1 -C 6 alkyl, aryl radical or C 1 -C 6 alkoxy; or —NR 3 R 4 ,  
     wherein  
     R 3  and R 4  are each independently of the other hydrogen, unsubstituted or substituted aryl radical or C 1 -C 6 alkyl, and  
     R 2  is hydrogen, hydroxyl, unsubstituted or substituted C 1 -C 6 alkyl, aryl radical or C 1 -C 6 alkoxy, —NR 3 R 4 , or an organic radical of formula (2)  
                 
 
     wherein  
     R 5  is hydrogen, unsubstituted or substituted aryl radical or C 1 -C 6 alkyl, and  
     X −  is an anion.  
     Further, the present invention relates to compositions thereof, especially comprising other dyes, to processes for the preparation thereof and to the use thereof in the dyeing of organic material, such as keratin, wool, leather, silk, cellulose or polyamides, and preferably human hair.

[0001] The present invention relates to novel cationic dyes,compositions thereof, to processes for their preparation and to theiruse in the dyeing of organic material, such as keratin fibers, wool,leather, silk, cellulose or polyamides, especially keratin-containingfibers, cotton or nylon, and preferably hair, more preferably humanhair.

[0002] It is known, for example, from WO 95/01772, WO 95/15144, EP 714954 and EP 318 294 that cationic dyes can be used to dye organicmaterial, for example keratin, silk, cellulose or cellulose derivatives,and also synthetic fibers, for example polyamides. Cationic dyes exhibitvery brilliant shades. A disadvantage is their unsatisfactory fastnessto hydrolysis and to light, their frequently inadequate stability underreducing or oxidizing conditions, and their frequently unsatisfactorystorage stability (see: John F. Corbett: “The Chemistry of Hair-CareProducts”, JSCD August 1976, page 290).

[0003] The actual technical problem of the present invention was toprovide brilliant dyes that are distinguished by deep dying having goodfastness properties with respect to washing, light, shampooing andrubbing, and that preferably exhibit satisfactory stability underreducing or oxidizing dyeing conditions, for the dyeing of organicmaterial.

[0004] Accordingly, the cationic dye of formula (1)

[0005] has been discovered,

[0006] wherein

[0007] R₁ and R₇ are each independently of the other hydrogen, hydroxyl;unsubstituted or substituted C₁-C₆alkyl, aryl radical or C₁-C₆alkoxy; or—NR₃R₄,

[0008] wherein

[0009] R₃ and R₄ are each independently of the other hydrogen,unsubstituted or substituted aryl radical or C₁-C₆alkyl, and

[0010] R₂ is hydrogen, hydroxyl, unsubstituted or substitutedC₁-C₆alkyl, aryl radical or C₁-C₆alkoxy, —NR₃R₄, or an organic radicalof formula (2)

[0011] wherein

[0012] R₅ is hydrogen, unsubstituted or substituted aryl radical orC₁-C₆alkyl, and

[0013] X⁻ is an anion.

[0014] Preferred is a cationic dye of formula (1), wherein

[0015] R₁ and R₇ are each independently of the other hydrogen,unsubstituted C₁-C₆alkyl, -(C₁-C₆alkylen)—OH, —(C₁-C₆alkylen)—NR₃R₄ or—NR₃R₄, wherein

[0016] R₃ and R₄ are each independently of the other hydrogen,unsubstituted C₁-C₆alkyl, and

[0017] R₂ is hydrogen, hydroxyl, unsubstituted C₁-C₆alkyl,—(C₁-C₆alkylen)—OH, —(C₁-C₆alkylen)-NR₃R₄; or —NR₃R₄, or an organicradical of formula (2).

[0018] Further, preference is given to a cationic dye of formula (1),wherein R₁, R₂ and R₇ are the same substituents, such as hydrogen,unsubstituted C₁-C₆alkyl, —(C₁-C₆alkylen)—OH, or —(C₁-C₆alkylen)—NR₃R₄.

[0019] More preferred is a cationic dye of formula (1), wherein

[0020] R₁ and R₇ are hydrogen.

[0021] In the present invention, substituents of C₁-C₆alkyl, aryl orbenzyl are, for example hydroxyl, NR₃R₄, wherein

[0022] R₃ and R₄ are each independently of the other hydrogen,unsubstituted or substituted aryl radical or C₁-C₆alkyl; or

[0023] C₁-C₈alkyl, C₁-C₈alkoxy, cyanide and/or halide.

[0024] The alkyl radical is, for example, C₁-C₈alkyl, C₁-C₆alkyl andpreferably C₁-C₄alkyl, and may be straight-chain, branched, substitutedor unsubstituted, or, from C₅alkyl upwards, monocyclic or polycyclic,and may be uninterrupted or interrupted by hetero atoms, such as O, S,N, NH; for example —CH₂CH₂—O— CH₂CH₂—O— CH₂CH₃, or —CH₂CH₂—O— CH₂CH₃, or—CH₂CH₂—O—CH₃, or —CH₂—O—CH₃.

[0025] C₁-C₈alkyl is, for example, methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2′-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl,1,1′,3,3′-tetramethylbutyl or 2-ethylhexyl.

[0026] C₁-C₆alkyl is, for example, methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2′-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl.

[0027] C₁-C₄alkyl is, for example, methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl or tert-butyl.

[0028] C₁-C₆alkoxy is O—C₁-C₆alkyl, preferably O—C₁-C₄alkyl.

[0029] Aryl radical is, for example, an unsubstituted or substitutedphenyl, benzyl- or tolyl

[0030] Halide is, for example, fluoride, chloride, bromide or iodide,especially chloride and fluoride.

[0031] “Anion” denotes, for example, an organic or inorganic anion, suchas halide, preferably chloride and fluoride, sulfate, hydrogen sulfate,phosphate, boron tetrafluoride, carbonate, bicarbonate, oxalate orC₁-C₈alkyl sulfate, especially methyl sulfate or ethyl sulfate; anionalso denotes lactate, formate, acetate, propionate or a complex anion,such as the zinc chloride double salt.

[0032] The anion is especially a halide, preferably chloride orfluoride, sulfate, hydrogen sulfate, methylsulfate, phosphate, formate,acetate or lactate.

[0033] The anion is more especially chloride, methyl sulfate, formate oracetate.

[0034] Most preference is given to cationic dyes of formula (3), (4),(5), (6) or (7)

[0035] wherein

[0036] X⁻ is an anion.

[0037] The present invention relates also to a process for thepreparation of the dyes of formula (1), preferably to a dye of formula(3), (4), (5), (6) or (7) and comprises reacting a compound of formula(8), which is obtainable according to methods known, such as describedin T. Deligeorgiev at al in “Dyes and Pigments”, Vol. 31(3), pages 219to 224, from 1996,

[0038] wherein

[0039] R₆ is C₁-C₆alkoxy or halide, preferred halides are chloride orfluoride, and

[0040] X⁻ is an anion,

[0041] with an amine of formula (9)

[0042] wherein

[0043] R₁, R₅ and R₇ are each independently of the other hydrogen,hydroxyl; unsubstituted or substituted C₁-C₆alkyl, aryl radical orC₁-C₆alkoxy; or —NR₃R₄,

[0044] wherein

[0045] R₃ and R₄ are each independently of the other hydrogen,C₁-C₆alkyl, unsubstituted or substituted aryl radical, preferably R₃ andR₄ are each independently of the other hydrogen, C₁-C₆alkyl,

[0046] preferably, wherein R₁ is hydrogen; and

[0047] X⁻ is an anion.

[0048] The reaction is generally initiated by bringing the compound offormula (8) and the amine of formula (9) into contact; for example bymixing together the starting compounds or by drop wise addition of onestarting compound to the other.

[0049] Customary, the temperature is in the range of 290 to 300 K duringthe mixing of the starting compounds.

[0050] The molar ratio of compound of formula (8) to amine of formula(9) is generally selected in the range from 5:1 to 1:5, especially inthe range from 3:1 to 1:3, more especially in the range from 2:1 to 1:1.

[0051] The duration of reaction is generally dependent on the reactivityof the starting compounds, on the reaction temperature chosen and on thedesired conversion. The chosen duration of reaction is usually in therange from one hour to three days.

[0052] The reaction temperature for the reaction of the compound offormula (8) with the amine of formula (9) is advisable to select in therange from 293 to 363K, especially in the range from 323 to 355K, moreespecially in the range from 333 to 355K.

[0053] The reaction pressure chosen is generally in the range from 70kPa to 10 MPa, especially from 90 kPa to 5 MPa, and is more especiallyatmospheric pressure.

[0054] It may by desirable to conduct the reaction of compound offormula (8) and amine of formula (9) in the presence of a catalyst.

[0055] The molar ratio of compound of formula (8) to the catalyst isgenerally selected in the range from 10:1 to 1:5, especially in therange from 10:1 to 1:1.

[0056] Suitable catalysts are for example an alkali metalC₁-C₆alkyloxide, such as sodium-, potassium or lithium C₁-C₆alkyloxide,preferably sodium methoxide, potassium methoxide or lithium methoxide,or sodium ethoxide, potassium ethoxide or lithium ethoxide; or tertiaryamines, for example, such as pyridine, trimethylamine, triethylamine,trioctyllamine, 1,4-diazabicyclo[2.2.2]octan, chinuclidine,N-methylpiperidine; or alkalimetal acetate, for example such as sodiumacetate, potassium acetate, or lithium acetate. Preferred are potassiumacetate, sodium methoxide, pyridine and 1,4-diaza-bicyclo[2.2.2]octan.

[0057] It is recommended that the reaction mixture obtained besubsequently stirred in the selected temperature range from 293 to 363K, especially in the range from 323 to 355K, more especially in therange from 333 to 355K. The duration chosen for the subsequent stirringis generally from 1 hour to 24 hours.

[0058] In addition, the reaction can be carried out with or withoutsolvent, but is preferably carried out in a solvent. Preference is givento organic solvents or solvent mixtures.

[0059] Within the context of this invention, solvents are organicsolvents and water, or a mixture of organic solvents or a mixture oforganic solvents and water. Organic solvents are, for example, protic oraprotic polare organic solvents, such as alcohols, for example methanol,ethanol, n-propanol, isopropanol, butanol or glycols, especiallyisopropanol, or nitrile, such as acetonitrile or propionitrile, oramide, such as dimethylformamide, dimethylacetamide or N-methylpyridine,or sulfoxide, such as dimethylsulfoxide, or mixtures thereof.

[0060] The ratio by weight of compound of formula (8) to the solvent isgenerally in the range from 20 to 90% by weight, especially in the rangefrom 30 to 60% by weight.

[0061] The prepared product may be advantageously worked up andisolated, and if desired be purified.

[0062] Customary, the work up starts by decreasing the temperature ofthe reaction mixture in the range from 280 to 300 K, especially in therange from 290 to 300 K.

[0063] It may be of advantageous to decrease the temperature slowly,over a period of several hours.

[0064] In general, the reaction product is usually filtered and thenwashed with water or a salt solution and subsequently dried.

[0065] Filtration is normally carried out in standard filteringequipment, for example Büchner funnels, filter presses, pressurisedsuction filters, preferably in vacuo.

[0066] The temperature for the drying is dependent on the pressureapplied. Drying is usually carried out in vacuo at 50-200 mbar.

[0067] The drying is usually carried out at a temperature in the rangefrom 313 to 363 K, especially from 323 to 353 K, and more especially inthe range from 328 to 348 K.

[0068] It has proved advantageous for the product to be purified byrecrystallisation after it has been isolated.

[0069] Organic solvents and solvent mixtures are suitable for therecrystallisation. Preference is given to alcohols, for examplemethanol, ethanol, 2-propanol or butanol, especially 2-propanol.

[0070] The dyes of formula (1) according to the invention are suitablefor dyeing organic material, such as keratin, wool, leather, silk,cellulose or polyamides, especially keratin-containing fibers, cotton ornylon, and preferably human hair.

[0071] The multiplicity of shades of the dye, which results by themethod according to the present invention, can be increased bycombination with other dyes. The present invention relates also to thecoloration of hair with a dye of formula (1) according to the presentinvention, and at least a single further dye.

[0072] The dye of formula (1) of the present invention can be combinedwith dyes of the same or different class of dyes, especially with directdyes, oxidation dyes; dye precursor combinations of a coupler compoundand a diazotized compound, or a capped diazotized compound; and/orcationic reactive dyes.

[0073] Direct dyes are natural or synthetic; they are uncharged,cationic or anionic, such as acid dyes.

[0074] Oxidation dye denotes also for oxidation dye precursors, whichare from the group of the developer and coupler compounds. Wherein thecoupler compounds denotes also to the addition salts thereof with anacid.

[0075] In the context of the present invention the single classes ofdyes comprise the dyes defined in the Color Index of the Society ofTextile Chemist and Colorist.

[0076] Further, in the context of the present invention, combinationscomprising of a compound of formula (1) are compositions, formulation,methods and.

[0077] One preferred embodiment of the present invention is thecombination of at least a single compound of formula (1) with a directdye, which are described in “Dermatology”, edited by Ch. Culnan, H.Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch.Zviak, The Science of Hair Care, chapter 7, pages 248-250, and in“Europäisches Inventar der Kosmetikrohstoffe”, 1996, published by TheEuropean Commission, obtainable in diskette form from the Bundesverbandder deutschen Industrie-und Handelsuntemehmen für Arzneimittel,Reformwaren und Körperpflegemittel e.V., Mannheim.

[0078] More preferred direct dyes for the combination with at least asingle compound of formula (1), especially for semi permanent dyeing,are:

[0079] 2-Amino-3-nitrophenol, 2-Amino-4-hydroxyethylamino-anisolesulfate, 2-Amino-6-chloro-4-nitrophenol,2-Chloro-5-nitro-N-hydroxyethylene-p-phenylendiamine,2-Hydroxyethyl-picramic acid,2,6-Diamino-3-((pyridine-3yl)-azo)pyridine,2-Nitro-5-glyceryl-methylaniline, 3-Methylamino-4-nitro-phenoxyethanol,4-Amino-2-nitrodiphenyleneamine-2′-carboxilic acid,6-Nitro-1,2,3,4,-tetrahydroquinoxaline,4-N-Ethyl-1,4-bis(2′-hydroxyethylamino-2-nitrobenzene hydrochloride,1-Methyl-3-nitro-4-(2′-hydroxyethyl)-aminobenzene,3-Nitro-p-hydroxyethyl-aminophenol, 4-Amino-3-nitrophenol,4-Hydroxypropylamine-3-nitrophenol, Hydroxyanthryl-aminopropylmethylmorphlino methosulfat, 4-Nitrophenyl-aminoethylurea,6-Nitro-p-toluidine, Acid Blue 62, Acid Blue 9, Acid Red 35, Acid Red 87(Eosin), Acid Violet 43, Acid Yellow 1, Basic Blue 3, Basic Blue 6,Basic Blue 7, Basic Blue 9, Basic Blue 12, Basic Blue 26, Basic Blue 99,Basic Brown 16, Basic Brown 17, Basic Red 2, Basic Red 22, Basic Red 76,Basic Violet 14, Basic Yellow 57, Basic Yellow 9, Disperse Blue 3,Disperse Orange 3, Disperse Red 17, Disperse Violet 1, Disperse Violet4, Disperse Black 9, Fast Green FCF, HC Blue 2, HC Blue 7, HC Blue 8, HCBlue 12, HC Orange 1, HC Orange 2, HC Red 1, HC Red 10-11, HC Red 13, HCRed 16, HC Red 3, HC Red BN, HC Red 7, HC Violet 1, HC Violet 2, HCYellow 2, HC Yellow 5, HC Yellow 5, HC Yellow 6, HC Yellow 7, HC Yellow9, HC Yellow 12, HC Red 8, Hydroxyethyl-2-nitro-p-toluidine,N,N-Bis-(2-Hydroxyethyl)-2-nitro-p-phenylendiamine, HC Violet BS,Picramic Acid, Solvent Green 7.

[0080] More preferred are combinations with cationic azo dyes, forexample according to GB-A-2 319 776 as well as the oxazine dyesdescribed in DE-A-299 12 327 and mixtures thereof with the other directdyes mentioned therein.

[0081] Preferred direct dyes for the combination with at least a singlecompound of formula (1) or a combination of at least a single compoundof formula (1) and oxidative dyes and oxidization agents, especially forsemi permanent dyeing and permanent dyeing, are: Disperse Violet 4,Picramic acid, N,N′-Bis-(2-Hydroxyethyl)-2-nitro-p-phenylendiamine, HCYellow No. 5, HC Blue No. 2, HC Yellow No. 2,2-Chloro-5-nitro-N-hydroxyethyl-p-phenylendiamine, HC Red No. 3,4-Amino-3-nitrophenol, Basic Blue 99, 2-Hydroxyethyl Picramic acid, HCYellow No. 6, Hydroxyethyl-2-nitro-p-toluidine,2-Amino-6-chloro-4-nitrophenol, 4-Hydroxypropylamino-3-nitrophenol,Basic Red 2, HC Red No. 16 and HC Blue No. 16.

[0082] Further preferred cationic dyes for the combination with acompound of formula (1) according to the present invention are describedin the following references

[0083] in WO 95/01772, especially on page 2, line 7 to page 4, line 1,and especially on page 4, line 35 to page 8, line 21 and on pages 11 to27, or

[0084] in WO 01/66646, especially on page 1, line 18 to page 3, line 16,and preferred from page 16, line 20 to page 22, and cationic dyes asdescribed on pages 10 to 17, or

[0085] in EP 970 685, especially on page 2, line 44 to page 9, line 56and preferably on page 9, line 58 to page 48, line 12, or

[0086] direct dyes are described in DE-A-19 713 698, especially page 2,line 61 to page 3, line 43, or

[0087] direct dyes and oxidizing agent are described in WO 97/20545,especially on page 1, lines 4 to 10, in particular on page 3, lines 24to 32, and on page 11, line 6 to page 13, line 19, especially withdirect dyes are described on page 5, line 28 to page 8, line 20, orcationic dyes and anionic UV-absorbers are described in EP 1 166 752,especially on page 3, line 20 to page 4, line 21, in particular with UVabsorber on page 4, lines 26 to 3, and especially on page 7, line 47 topage 9, line 56.

[0088] More preferred for a combination with a cationic dye of formula(1) are cationic dyes, such as Basic Yellow 87, Basic Orange 31 or BasicRed 51, or cationic dyes as described in WO 01/66646, especiallycationic dye of example 4, or cationic dyes as described in WO 02/31056,especially cationic dye of example 6, compound of formula 106, orcationic dye of formula (3) as described in EP-A-714,954 or a yellowcationic dyes of formula (I)

[0089] wherein

[0090] R₁ and R₂ are each independently of the other a C₁-C₈alkylradical or an unsubstituted or substituted benzyl radical,

[0091] R₃ is hydrogen, C₁-C₈alkyl, C₁-C₈alkoxy, cyanide or halide,preferably hydrogen, and

[0092] X⁻ is an anion, and preferably a compound of formula (I)

[0093] wherein

[0094] R₁ is methyl, R₂ is benzyl, R₃ is hydrogen, and X⁻ is an anion,or

[0095] wherein

[0096] R₁ is benzyl, R₂ is benzyl, R₃ is hydrogen, and X⁻ is an anion,or

[0097] wherein

[0098] R₁ is benzyl, R₂ is methyl, R₃ is hydrogen, and X⁻ is an anion.

[0099] The process for the preparation of compounds of formula (I)comprises reacting a substituted or unsubstituted phenylhydrazine with a4-pyridylaldehyde in the presence of an acid to form a hydrazone, whichis optionally alkylated or benzylated.

[0100] Further preferred for a combination with a cationic dye offormula (1) are cationic nitroaniline and anthraquinone dyes for thecombination a compound of formula (1) according to the invention, forexample those described in the following patent specifications: U.S.Pat. No. 5,298,029, especially in column 2, line 33 to column 5, line38; U.S. Pat. No. 5,360,930, especially in column 2, line 38 to column5, line 49; U.S. Pat. No. 5,169,403, especially in column 2, line 30 tocolumn 5, line 38; U.S. Pat. No. 5,256,823, especially in column 4, line23 to column 5, line 15; U.S. Pat. No. 5,135,543, especially in column4, line 24 to column 5, line 16; EP-A-818 193, especially on page 2,line 40 to page 3, line 26; U.S. Pat. No. 5,486,629, especially incolumn 2, line 34 to column 5, line 29; and EP-A-758 547, especially onpage 7, line 48 to page 8, line 19.

[0101] In addition, preferred are combinations of a compound of formula(1) according to the invention with further cationic dyes or with otherdyes. Preferred are mixtures as given in the below references, with theproviso that one cationic dye is replaced by a compound of formula (1)according to the present invention.

[0102] mixtures of at least two cationic dyes as described in WO95/01772, especially on page 8, line 34 to page 10, line 22 with thegiven preferences, or

[0103] combinations of Pyrazolo-[1,5-a]-pyrimidines with at least onecationic dye as described in EP 998,908, especially on page 2, line 34to line 42, with preferred Pyrazolo-[1,5-a]-pyrimidines as described inEP 998,908, especially on page 2, line 48 to page 4, line 3, and withpreferred cationic direct dyes as described in EP 998,908, especially onpage 4, line 22 to page 47, line 24, or

[0104] combinations of cationic dyes as described in FR-2788432,especially on page 53, line 1 to page 63, line 23, especially acombination of cationic dyes with Arianors in FR-2788432, especially onpages 51 to 52, or especially a combination with at least one BasicBrown 17, Basic brown 16, Basic Red 76 and Basic Red 118, and/or atleast one Basic Yellow 57, and/or at least one Basic Blue 99, or

[0105] combinations of direct dyes and/or an oxidation dye and oxidizingagents in the form of permanent-wave fixing solution, especially withdirect dyes as described in DE-A-19 713 698, especially page 4, line 65to page 35, line 59, or

[0106] combinations of cationic dyes and an oxidation dye of thedeveloper compound type and oxidizing agents as described in EP 850 638,especially on page 2, line 27 to page 7, line 46 and preferred on page7, line 20 to page 9, line 26, or

[0107] combinations of an extemporaneous mixture of a composition (A)containing one or more oxidation dye precursors and optionally one ormore couplers, and of a composition (B), in powder form, containing oneor more direct dye, preferably cationic, optionally dispersed in anorganic pulverulent excipient and/or a mineral pulverulent excipient,and a composition (C) containing one or more oxidizing agent asdescribed in U.S. Pat. No. 6,190,421, especially in column 2, lines 2 to1, and preferably with oxidation dye precursors as described in column2, line 35 to column 5, line 13, and preferably with direct dyes asdescribed in column 5, line 30 to column 7, line 14, or

[0108] a ready-to-use composition comprising, at least one oxidationbase, at least one cationic direct dye and at least one enzyme of2-electron oxidoreductase type in the presence of at least one donor forthe said enzyme as described in U.S. Pat. No. 6,228,129, especially incolumn 26, line 26 to column 27, line 9 with cationic direct dyes asdescribed in column 8, line 17 to column 13, line 65, especially thoseas described in column 20, line 11 to line 19, in column 23, line 61 tocolumn 24, line 25, or

[0109] compositions of at least one direct cationic dye and at least onenitrated benzene dye as described in WO 99/20235 on page 2, line 1 topage 7, line 9, and on page 39, line 1 to page 40b line 11, withcationic direct dyes as described on page 8, line 12 to page 25 line 6,and nitro benzene direct dyes as described on page 26, line 7 to page30, line 15, or compositions of at least one direct cationic dye and atleast one autooxidisable oxidation dye, especially benzene, indol andindoline derivatives as described in WO 99/20234, with in preferreddirect dyes as given on page 2, line 17 to page 26, line 4, andautooxidisable oxidation dye as described especially on page 26, line 10to page 28, line 15, or

[0110] oxidation dyeing compositions of at least one direct dye and atleast one meta-Aminophenol derivative and at least one developercompound and an oxidizing agent as described in EP 850 636, especiallyon page 5, line 41 to page 7, line 52, and preferably on page 19, line50 to page 22, line 12, with preferred direct dye as described on page18, lines 1 and 2 in connection with page 7, line 53 to page 17, line55, and with preferred meta-Aminophenol derivatives as described on page7, line 47 to line 52, and with preferred developer compounds asdescribed on page 6, line 10 to page 7, line 46, or

[0111] oxidation dyeing compositions of at least one direct dye and atleast one developer compound selected from the group ofpara-Phenylenediamine derivatives and Bis-Phenylalkylenediamine and, andat least one coupler compound selected from the group of meta-Diphenolsand an oxidizing agent, as described in EP-A-850 637, especially on page6, line 50 to page 8, line 44,

[0112] oxidation dyeing compositions with cationic couplers, asdescribed in WO 99/48856, especially on page 9, line 16 to page 13, line8, and page 11, line 20 to page 12, line 13, or

[0113] cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives,as described in EP 998 908, especially on page 2, line 34 to page 4,line 23, or

[0114] arianoren and/or oxidative dyes, as described in FR-2 788 432,especially on page 2, line 16 to page 3, line 16, and page 5, line 19 topage 14, line 8, and combinations with cationic dyes as described onpage 14, line 23 and following, or

[0115] oxidative dye precursors (unsaturated aldehyde and couplercompounds), as described in German Patent Application 197 172 24,especially unsaturated aldehydes as described on page 2, line 50 to line66 and page 3 line 8 to line 12 are used as developer compounds, and

[0116] primary and secondary amino group compounds, nitrogen-containingheterocyclic compounds, amino acids, oligopeptids, aromatic hydroxycompounds, CH-active compounds as described on page 3, line 42 to page 5line 25 are used as coupler compounds.

[0117] Further preferred for the combination with a compound of formula(1) are cationic azo dyes, e.g. according to GB-A-2 319 776, as well asthe oxazine dyes described in DE-A-29 912 327 and mixtures thereof withthe other direct dyes mentioned therein.

[0118] More preferred for a combination with a cationic dye of formula(1) are cationic dyes such as Basic Yellow 87, Basic Orange 31 or BasicRed 51, or as described in WO 01/66646, especially cationic dye ofexample 4, or as described in WO 02/31056, especially cationic dye ofexample 6, compound of formula 106.

[0119] Especially preferred for a combination with a cationic dye offormula (1) are direct dye mixtures comprising a dye of formula (1) ofWO 01/66646, especially a direct dye of example 4, and/or or a dye offormula (2) of WO 02/31056, especially a direct dye of example 6, and/orBasic Yellow 87, and/or Basic Red 51, and/or Basic Orange 31.

[0120] No particular limitation is imposed on the acid dye used in thepresent invention so far as it is a water-soluble acid dye.

[0121] A further embodiment of the present invention concerns thecombination of a compound of formula (1) according to the invention withacid dyes, for example from the group of the compounds known by theinternational names (Color index), or trade names.

[0122] Preferred acid dyes for a combination with a cationic dye offormula (1) are described in U.S. Pat. No. 6,248,314, they include RedColor No. 120, Yellow Color No. 4, Yellow Color No. 5, Red Color No.201, Red Color No. 227, Orange Color No. 205, Brown Color No. 201, RedColor No. 502, Red Color No. 503, Red Color No. 504, Red Color No. 506,Orange Color No. 402, Yellow Color No. 402, Yellow Color No. 406, YellowColor No. 407, Red Color No. 213, Red Color No. 214, Red Color No. 3,Red Color No. 104, Red Color No. 105(1), Red Color No. 106, Green ColorNo. 2, Green Color No. 3, Orange Color No. 207, Yellow Color No. 202(1),Yellow Color No. 202(2), Blue Color No. 202, Blue Color No. 203, BlueColor No. 205, Blue Color No. 2, Yellow Color No. 203, Blue Color No.201, Green Color No. 201, Blue Color NO. 1, Red Color No. 230(1), RedColor No. 231, Red Color No. 232, Green Color No. 204, Green Color No.205, Red Color No. 401, Yellow Color No. 403(1), Green Color No. 401,Green Color No. 402, Black Color No. 401 and Purple Color No. 401,especially Black Color No. 401, Purple Color 401, Orange Color No. 205.

[0123] These acid dyes may be used either single or in any combinationthereof.

[0124] Preferably they are incorporated in dyeing composition for humanhair in a proportion of 0.001-5% by weight (hereinafter indicated merelyby “%”), particularly 0.005-4%, more particularly 0.2-3% based on thetotal weight of the composition, from the viewpoint of practical use inthat a sufficient hair-dyeing effect is achieved, and the hand skin isscarcely smeared.

[0125] A further embodiment of the present invention concerns thecombination of a compound of formula (1) according to the invention withuncharged dyes, for example from the group of the nitroanilines,nitrophenylenediamines, nitroaminophenols, anthraquinones, indophenols,phenazines, phenothiazines, bispyrazolons or bispyrazol aza derivativesor methines.

[0126] In addition, the present invention concerns the combination of acompound of formula (1) according to the invention with oxidation dyes.

[0127] Suitable oxidation dyes are described for example in

[0128] German Patent Application 19 94 450, especially on page 6, line 6to line 64, or

[0129] German Patent Application 19 959 479, especially in column 2,line 6 to column 3, line 11, or

[0130] in the series “Dermatology”, edited by Ch. Culnan, H. Maibach,Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, TheScience of Hair Care, chapter 8, on pages 264-267 (oxidation dyes), or

[0131] in German Patent Application 19 717 224; unsaturated aldehydes asdescribed on page 2, line 50 to line 66 and on page 3 line 8 to line 12are used as developer compounds, and primary and secondary amino groupcompounds, nitrogen-containing heterocyclic compounds, amino acids,oligopeptids, aromatic hydroxy compounds, CH-active compounds asdescribed on page 3, line 42 to page 5 line 8 are used as couplercompounds.

[0132] Preferred oxidation dye precursors of the developer type for acombination with a cationic dye of formula (1) are for example primaryaromatic amines, which are substituted in the para- or ortho- positionwith a substituted or unsubstituted hydroxy- or amino residue, ordiaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolderivatives, 2,4,5,6-tetraaminopyrimidin derivatives, or unsaturatedaldehydes as described in German Patent Application 19 717 224,especially on page 2, line 50 to line 66 and on page 3 line 8 to line12, or cationic developer compounds as described in WO 00/43367,especially on page, 2 line 27 to page 8, line 24, in particular on page9, line 22 to page 11, line 6. Also very suitable for a combination witha cationic dye of formula (1) according to the invention are developerdyes in their physiological compatible acid addition salt form, such ashydrochloride or sulfate. Developer dyes, which have aromatic OHsubstituents are also suitable in their salt form with base, such asalkalimetalphenolates.

[0133] Preferred developer compounds are:

[0134] 1,4-diamino-benzene (p-phenylendiamine),1,4-diamino-2-methyl-benzene (p-toluylen-diamine),1,4-diamino-2,6-dimethyl-benzene, 1,4-diamino-2,5-dimethyl-benzene,1,4-diamino-2,3-dimethyl-benzene, 2-chloro-1,4-diaminobenzene,4-phenylamino-aniline, 4-di-methylamino-aniline, 4-diethylamino-aniline,hydroxyethyl-p-phenylendiamine, 1-(2′-hydroxy-ethyl)-2,5-diaminobenzene,N,N-bis-(2-hydroxyethyl)-p-phenylendiamine,4-[(2-methoxyethyl-)amino]-aniline, 4-[(3-hydroxypropyl)amino]-aniline,hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine)hydrochloride,1,4-diamino-2-(2-hydroxyethyl)-benzene, 1,4-diamino-2-(1-methylethyl)-benzene, 2-(2,5-diaminophenoxy)-ethanol,1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol,bis-(2-hydroxy-5-aminophenyl)-methane,1,4-bis-(4-aminophenyl)-diazacycloheptane,1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctan,1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane,hydroxyethyl-3,4-methylenedioxyaniline, p-aminophenol, o-aminophenol,m-aminophenol, 2-amino-6-methyl-phenol, 4-methylaminophenol sulfate,4-amino-m-cresol, 6-amino-m-cresol, 6-amino-m-cresol,2-amino-4-hydroxyethylaminoanisole, 2-amino-5-methyl-phenol,4-amino-3-methylphenol, 4-methylamino-phenol,2-aminomethyl-4-aminophenol,4-amino-2-[(2-hydroxyethyl)-amino]methyl-phenol,4-amino-2-(2-hydroxyethoxy)-phenol, 4-amino-2-(methoxymethyl)-phenol,4-amino-2-(2-hydroxyethyl)-phenol, 2-hydroxymethylamino-4-aminophenol,bis-(4-aminophenyl)amine, 4-amino-3-fluorphenol,2-hydroxymethyl-4-aminophenol, 4-amino-2-(diethylamino)-methyl)-phenol,5-amino-salicylsäure, 2,5-diamino-pyridine, 2-amino-3-hydroxy-pyridine,2,6-dimethoxy-3,5-diamino-pyridine, 2,4,5,6-tetraaminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2,4-dihydroxy-5,6-diaminopyrimidine,2-dimethylamino-4,5,6-triaminopyrimidine,2,5,6-triamino-4-(1H)-pyrimi-done, further 4,5-diaminopyrazolderivatives as described in EP 0 740 741 or WO 94/08970, especially4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazol,4,5-diamino-1-(1-methylethyl)-1H-pyrazol,4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazol,1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazol,4,5-diamino-1-methyl-1H-pyrazol.

[0135] More preferred developer dyes are p-phenylendiamine,p-toluylendiamine, p-aminophenol, m-aminophenol, o-aminophenol,N,N-bis-(2-hydroxyethyl)-p-phenylendiamine sulfate,2-amino-4-hydroxyethylaminoanisole sulfate,hydroxyethyl-3,4-methylenedioxyaniline,1-(2′-hydroxyethyl)-2,5-diaminobenzene,2,6-dimethoxy-3,5-diamino-pyridine,hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine)hydrochloride,hydroxyethyl-p-phenylendiamine sulfate, 4-amino-3-methylphenol,4-methylaminophenol sulfate, 2-aminomethyl-4-aminophenol,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazol, 4-amino-m-cresol,6-amino-m-cresol, 5-amino-6-chloro-cresol, 2,4,5,6-tetraaminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidinesulfate.

[0136] Preferred oxidation dye precursors of the coupler type for acombination with a cationic dye of formula (1) are for examplem-phenylendiamine derivatives, naphthole, resorcine and resorcinederivatives, pyrazolone and m-aminophenol derivatives.

[0137] Especially preferred coupler compounds for a combination with acationic dye of formula (1) are N-(3-dimethylamino-phenyl)-urea,4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol,2,4-diaminophenoxyethanol, 2-amino-4-[(2-hydroxyethyl)amino]-anisole,p-aminophenol, m-aminophenol and its derivatives, especially5-amino-2-methylphenol, 5-(3-hydroxypropylamino)-2-methylphenol,3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol,2,6-dimethyl-3-aminophenol,3-trifluoroacetylamino-2-chloro-6-methylphenol,5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methyl-phenol,5-(2′-hydroxyethyl)-amino-2-methylphenol, 3-(diethylamino)-phenol,N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-(methylamino)-benzene,3-(ethylamino)-4-methylphenol and 2,4-dichloro-3-aminophenol, or

[0138] o-aminophenol and its derivatives, such as5-methyl-2-(1-methylamino)-phenol, 3-di-methylamino-phenol,3-diethylamino-phenol, 5-amino-2-methyl-phenol,5-amino-4-fluor-2-methyl-phenol, 5-amino-4-methoxy-2-methyl-phenol,5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichlor-phenol,5-amino-2,4-dichlor-phenol, 3-amino-2-methyl-phenol,3-amino-2-chlor-6-methyl-phenol, 3-amino-phenol,2-[(3-hydroxyphenyl)amino]-acetamide,5-[(2-hydroxyethyl)amino]-2-methyl-phenol,3-[(2-hydroxyethyl)amino]-phenol, 3-[(2-methoxyethyl)amino]-phenol,5-amino-2-ethyl-phenol, 2-(4-amino-2-hydroxyphenoxy)-ethanol,5-[(3-hydroxypropyl)amino]-2-methyl-phenol,3-[(2,3-dihydroxypropyl)amino]-2-methyl-phenol,3-[(2-hydroxyethyl)amino]-2-methyl-phenol,

[0139] m-diaminobenzene and its derivatives such as2,4-diaminophenoxyethanol, 1,3-bis-(2,4-diaminophenoxy)-propane,1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,1,3-bis-(2,4-diaminophenyl)-propane, 3-[(2-aminoethyl)amino]-aniline,1,3-di(2,4-diaminophenoxy)-propane, 1,3-diamino-2,4-dimethoxy-benzene,2,6-bis(2-hydroxyethyl)amino-toluene, di(2,4-diaminophenoxy)-methane,3-[di(2-hydroxyethyl)amino]-aniline, 2,6-bis-(2-hydroxyethyl-amino)-1-methylbenzene and 1 -amino-3-bis-(2′-hydroxyethyl)-aminobenzene,o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and2,3-diamino-1-methylbenzene, 2,4-diamino-1-fluor-5-methyl-benzene,2,4-diamino-1-methoxy-5-methyl-benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylamino-benzene,2,4-diaminophenoxy-acetic acid, 2,4-diamino-1-ethoxy-5-methyl-benzene,3-[(2-hydroxyethyl)amino]-aniline, 3,4-diamino-benzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,6-amino-3,4-dihydro-1,4(2H)-benzoxazine,2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methyl-benzene,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxy-benzene2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxy-benzene,3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,6-amino-3,4-dihydro-1,4(2H)-benz-oxazine,

[0140] di- or trihydroxybenzene derivatives such as resorcine,resorcinmonomethylether, 2-methylresorcine, 5-methylresorcine,2,5-dimethyl resorcine, 1-chloro-2,4-dihydroxy-benzene,2-chlororesorcine, 4-chlororesorcine, 2,6-dihydroxyethylaminotoluene,1,2-dichlor-3,5-dihydroxy-4-methyl-benzene,1,5-dichlor-2,4-dihydroxy-benzene, 1,3-dihydroxy-2-methyl-benzene,pyrogallol and 1,2,4-trihydroxybenzene,

[0141] pyridine derivatives such as 2,6-diamino-pyridine,2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine,2-amino-5-chloro-3-hydroxypyridine, 5-amino-4-chloro-2-methyl-phenol,3-diamino-6-methoxy-pyridine, 3-amino-2-methylamino-6-methoxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine,2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine,2,6-diamino-3,5-dimethoxy-pyridine, and3,5-diamino-2,6-dimethoxypyridine,

[0142] naphthaline derivatives such as 1-naphthol, 2-methyl-1-naphthol,2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol,1,5-dihydroxynaphthaline, 1,6-dihydroxynaphthaline,

[0143] 1,7-dihydroxynaphthaline, 1,8-dihydroxynaphthaline,2,7-dihydroxynaphthaline and 2,3-dihydroxynaphthaline,2-methyl-1-naphthol-acetat,

[0144] morpholine derivatives such as 6-hydroxybenzomorpholine and6-aminobenzomorpholine, chinoxaline derivatives such as6-methyl-1,2,3,4-tetrahydrochinoxaline,

[0145] pyrazol derivatives such as -phenyl-3-methylpyrazol-5-one,3-methyl-1-phenyl-5-pyrazolone, indol derivatives such as4-hydroxyindol, 5-hydroxy-indol, 6-hydroxyindol and 7-hydroxyindol,2,3-indolindione, 5,6-dihydroxy-indol, 5,6-dihydroxy-indoline,

[0146] methylendioxybenzene derivates such as1-hydroxy-3,4-methylendioxybenzene, 1-amino-3,4-methylendioxybenzene and1-(2′-hydroxyethyl)-amino-3,4-methylendioxybenzene,3,4-methylendioxy-phenol, 3,4-methylendioxy-aniline,5-[(2-hydroxyethyl)amino]-1,3-benzodioxol,6-brom-1-hydroxy-3,4-methylendioxy-benzene, or

[0147] cationic coupler compounds as described in FR 2 794 644,especially on page 11, line 20 to page 15, line 34, and on page 17,lines 4 to 12, page 178, line 33 to page 18, line 24.

[0148] More especially preferred coupler compounds for a combinationwith a cationic dye of formula (1) are toluene-2,5-diamine sulfate,1-naphthol, 1,5-, 2,7-and 1,7-dihydroxy-naphthaline, 3-aminophenol,5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol,4-chlororesorcine, 2-chloro-6-methyl-3-aminophenol,2,6-dihydroxy-ethylaminotoluene, 2-methyl-5-dihydroxyethylaminophenol,2,4-diaminophenoxyethylol hydrochloride, 2-methylresorcine,5-methylresorcine, 2,5-dimethylresorcine, 3,4-methylenedioxyphenol,2-amino-4-hydroxyethylaminoanisole sulfate,2,6-di-(beta-hydroxy-ethylamino)-toluene, 4-amino-2-hydroxytoluene,6-hydroxyindol, 2-amino-3hydroxypyridine,2,6-dimethoxy-3,5-pyridinediamine hydrochloride and2,6-dihydroxy-3,4-dimethylpyridine.

[0149] Most preferred coupler compounds for a combination with acationic dye of formula (1) are 2-chloro-6-methyl-3-aminophenol,5-amino-2-methylphenol, 2-amino-3-hydroxypyridine,2,6-di-(beta-hydroxyethylamino)-toluol, 2-methylresorcine and1-naphthol.

[0150] Further, preferred for a combination with a cationic dye offormula (1) are:

[0151] the developer/-coupler combination 2,4,5,6-Tetraaminopyrimidineand 2-Methylresorcine are preferred for assessing of red shades, or

[0152] p-Toluenediamine and 4-Amino-2-hydroxytoluene for assessing ofblue-violet shades, or

[0153] p-Toluenediamine and 2-Amino-4-hydroxyethylaminoanisole forassessing of blue shades, or

[0154] p-Toluenediamine and 2,4-Diamino-phenoxyethynol for assessing ofblue shades, or

[0155] 3-Methyl-4-aminophenol and 4-Amino-2-hydroxytlouene for assessingof orange shades, or

[0156] p-Toluenediamine and resorcine for assessing of brown-greenshades, or

[0157] p-Toluenediamine and 1-Naphthol for assessing of blue-violetshades, or

[0158] p-Toluenediamine and 2-methylresorcine for assessing ofbrown-gold shades.

[0159] Further, one preferred embodiment of the present inventionconcerns the combination of a compound of formula (1) according to thepresent invention with autooxidizable compounds, such as, for examplebenzene, indol, or indoline, especially 5,6-dihydroxyindol or5,6-dihydroxyindoline derivatives as described in WO 99/20234,especially on page 26, line 10 to page 28, line 15, or in WO 00/28957 onpage 2, third paragraph.

[0160] Preferred autooxidizable benzene derivatives for a combinationwith a cationic dye of formula (1) are:

[0161] 1,2,4-trihydroxybenzene, 1-methyl-2,4,5-trihydroxybenzene,2,4-diamnio-6-methylphenol, 2-amino-4-methylaminophenol,2,5-diamino-4-methyl-phenol, 2,6-diamino-4-diethylamino-phenol,2,6-diamino-1,4-dihydroxybenzen, and the salts of these compounds, whichare accessible with acid.

[0162] Preferred autooxidizable indol derivatives for a combination witha cationic dye of formula (1) are:

[0163] 5,6-dihydroxyindol, 2-methyl-5,6-dihydroxyindol,3-methyl-5,6-dihydroxyindole, 1-methyl-5,6-dihydroxyindol,2,3-dimethyl-5,6-dihydroxyindol, 5-methoxy-6-dihydroxyindol,5-acetoxy-6-hydroixyindol, 5,6-diacetoxyindol, acid of5,6-dihydroxyindol-2-carbonacid, and the salts of these compounds, whichare accessible with acid.

[0164] Preferred autooxidizable indoline derivatives for a combinationwith a cationic dye of formula (1) are:

[0165] 5,6-dihydroxyindoline, 1-methyl-5,6-dihydroxyindoline,1-ethyl-5,6-dihydroxyindoline, and the salts of these compounds, whichare accessible with acid.

[0166] A compound of formula (1) according to the present invention canalso be combined with at least two different developers and at least onecoupler compound, or with at least two different couplers and at leastone developer compound. Such combinations are for example described inGerman Patent Application 197 172 24, especially on page 3, line 31 topage 5, line 8.

[0167] In addition, a compound of formula (1) according to the presentinvention may also be combined with naturally occurring dyes, such as,for example, henna red, henna neutral, henna black, camomile blossom,sandalwood, black tea, Rhamnus frangula bark, sage, campeche wood,madder root, catechu, sedre and alkanet root. Such coloring methods aredescribed, for example, in EP-A-404 868, especially on page 3, line 55to page 4, line 9.

[0168] Further, a compound of formula (1) may also be combined withcapped diazotised compounds.

[0169] Capped diazonium compounds that come into consideration include,for example, antidiazotates of formula

[0170] diazosulfonates of formula

[0171] triazenes of formula

[0172] and also cyclic triazenes of formula

[0173] In formula (22) to (25):

[0174] A is the radical of an unsubstituted or substituted, aromatic orheterocyclic aryl,

[0175] B is the radical of an unsubstituted or substituted,water-soluble, aliphatic or aromatic aryl and

[0176] R is an unsubstituted or substituted alkyl group,

[0177] it being necessary for at least one of the groups to contain awater-solubilising radical.

[0178] As a water-solubilising radical there comes into consideration,for example, SO₃H, COOH, OH or a quaternised ammonium radical of formula

[0179] wherein R₁, R₂ and R₃ are each independently of the othersunsubstituted or substituted alkyl and An is an anion.

[0180] According to the invention, alkyl groups R, R₁, R₂ and R₃ are tobe understood generally as open-chain or branched alkyl radicals, forexample methyl, ethyl, n- and iso-propyl or n-, sec- and tert-butyl.

[0181] Such alkyl radicals may be mono- or poly-substituted, for exampleby hydroxy, carboxy, halogen, cyano or C₁-C₄alkoxy.

[0182] Preferably, the alkyl groups are unsubstituted and each has from1 to 4, especially 1 or 2, carbon atoms.

[0183] As anion An there come into consideration both inorganic andorganic anions, for example halide, such as chloride, bromide or iodide,sulfate, hydrogen sulfate, methyl sulfate, formate, acetate or lactate.

[0184] The anion is generally governed by the preparation process.Preferably, it is chloride, hydrogen sulfate, sulfate, methosulfate oracetate.

[0185] A is the radical of an unsubstituted or substituted, aromatic orheterocyclic aryl. Suitable radicals include, for example, unsubstitutedor substituted radicals of benzene, radicals at position 1- or 2- ofnaphthalene, radical at position 2- of thiophene, radical at position2-of 1,3-thiazole, radical at position 5- of 1,2-thiazole, radical atposition 2-of 1,3-benzothiazole, radical at position 1- of2,3-benzothiazole, radical at position 2-of aminoimidazole, radical atposition 2-of 1,3,4-thiadiazole, radical at position 2-of1,3,5-thiadiazole, radical at position 2- of 1,3,4-triazole, radical atpositions 3-, 7- or 8-of pyrazole, radical at position 2-ofbenzimidazole, radical at position 2-of benzopyrazole, radical atpositions 2- or 4-of pyridine, radical at positions 2-, 3-, 4-, 7- or8-of quinoline, radical at position 2-of aminopyrimidine and radical atposition 3-of aminoisoxazole, radical at position 5-of aminoquinoline,radical at position 4-of aminodiphenylamine, radical at position 2-ofaminodiphenyl ether and radical at position 4-of aminoazobenzene.

[0186] Such radicals may be mono- or poly-substituted, for example byC₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, for example fluorine,bromine or chlorine, nitro, trifluoromethyl, CN, SCN,C₁-C₄alkylsulfonyl, phenylsulfonyl, benzylsulfonyl,di-C₁-C₄alkylaminosulfonyl, C₁-C₄-alkylcarbonylamino,C₁-C₄alkoxysulfonyl or by dihydroxy-C₁-C₄alkylaminosulfonyl.

[0187] B is the radical of an unsubstituted or substituted,water-soluble, aliphatic or aromatic aryl, suitable aliphatic arylsincluding especially those carrying a carboxylic acid or sulfonic acidgroup, for example starting materials for B radicals are:methylaminoacetic acid (sarcosine), methylaminobutyric acid,methylaminopropionic acid, ethylaminoacetic acid, ethylaminobutyricacid, 1-methylaminoethane-2-sulfonic acid, 1-ethylaminoethane-2-sulfonicacid and 1-methylaminopropane-3-sulfonic acid.

[0188] As starting materials for B radicals come into considerationespecially aniline compounds and aminonaphthalene compounds, especiallythose carrying a carboxylic acid or sulfonic acid group. The amino groupof such compounds may be unsubstituted but is preferably substituted,for example by unsubstituted or substituted C₁-C₄alkyl, suitablesubstituents thereof being especially hydroxy or carboxy.

[0189] Suitable coupling components include, for example, the couplingcomponents customarily used for azo dyes and known from the relevantliterature, for example those of the benzene series, the naphthaleneseries, the open-chain methylene-active compounds (for exampleacylacetarylamides) and the heterocyclic series.

[0190] The compounds of formula (22), (23), (24) and (25) are known, orcan be prepared in a manner known per se.

[0191] The compounds of formula (23) wherein B is the radical of analiphatic aryl are likewise known or can be prepared in a manner knownper se.

[0192] The compounds of formula (27)

[0193] wherein

[0194] A is the radical of an unsubstituted or substituted,water-soluble, aromatic or heterocyclic aryl,

[0195] B′ is the radical of an unsubstituted or substituted,water-soluble, aliphatic or aromatic aryl, and

[0196] R is an unsubstituted or substituted alkyl group, can likewise beprepared in a manner known per se.

[0197] For A and R, the definitions and preferred meanings indicated forformula (22) to (25) apply and, for B′, the definitions and preferredmeanings indicated for B in formula (22) to (25) apply in so far as theyrelate to aromatic amines.

[0198] The compounds of formula (27) can be prepared, for example, bydiazotising an amine of formula A-NH₂ in customary manner and couplingit to an amine of formula B′—NHR, there coming into consideration asamines B′—NHR only those compounds which couple at the nitrogen atom andnot at a carbon atom of the aromatic ring. Such compounds are preferablyaniline derivatives substituted in the 4 positions.

[0199] The present invention also describes formulations, which are usedfor the coloration of keratin fibers, especially human hair.

[0200] The formulations are applicable on human hair in differenttechnical forms. The specific technical form may be chosen in view ofthe envisaged application and/or dye or dye composition. Technical formsof formulation are for example a solution, especially a thickened wateryor watery alcoholic solution, a cream, foam, shampoo, powder, a gel, oran emulsion.

[0201] Preferred forms of formulations are ready to use compositions ora multi-compartment dyeing device or ‘kit’ or any of themulti-compartment packaging systems with compartments as described forexample as described in U.S. Pat. No. 6,190,421, column 2, lines 16 to31.

[0202] It is of advantage to prepare compositions of dyes, which are notstable to reduction, with oxidizing agent free compositions just beforethe dyeing process.

[0203] One preferred embodiment of the present invention concerns theformulation of dyes, especially those of formula (1) in powder form.

[0204] The coloring compositions according to the invention mayfurthermore comprise any active ingredient, additive or adjuvant knownfor such preparations.

[0205] Adjuvants that are suitable for such formulations are in generalcustomary in the field hair-coloring, such as for example surfactants ortensides, solvents, bases, acids, perfumes, polymeric adjuvant,thickeners and light stabilisers.

[0206] Preferred combinations of the coloring compositions according tothe invention with adjuvant used in the coloring of hair, are

[0207] combination of direct dyes with oxidizing agents to achievelightened coloration; wherein oxidizing agents especially described inWO 97/20545, especially page 9, lines 5 to 9, combination of direct dyesand/or an oxidation dye and oxidizing agents in the form ofpermanent-wave fixing solution, especially oxidizing agents as describedin DE-A-1 9 713 698, especially page 4, lines 52 to 55, or EP-A-1 062940, especially page 6, lines 41 to 47, (and in the equivalent WO99/40895),

[0208] oxidation dyes in the presence of oxidoreductase enzyme, asdescribed in WO 99/17730, especially page 4, line 11 to page 13, line28, and WO 99/36034, especially pages 3 to 15, combination of cationicdyes with polyols or polyethers; polyols or polyethers as described inEP-A-962 219, especially page 27, lines 14 to 38,

[0209] thickening polymers, as described in EP-A-970 684, especiallypage 48, line 16 to page 51, line 4,

[0210] sugar-containing polymers, as described in EP-A-970 687,especially page 28, line 17 to page 29, line 23,

[0211] quaternary ammonium salts, as described in WO 00/10517,especially page 44, line 16 to page 46, line 23,

[0212] anionic surfactants, as described in WO 00/10518, especially page45, line 11 to page 48, line 3,

[0213] non-ionic surfactants, as described in WO 00/10519, especiallypage 45, line 11 to page 50, line 12, or

[0214] silicones, as described in WO 00/12057, especially page 45, line9 to page 55, line 2. oxidative agent or laser and direct dyes, asdescribed in EP-920 856, especially on page 2, line 31 to page 53 line36, and on page 49, line 38 to page 50, line 41, with direct dyes asdescribed on page 3, line 54 to page 48, line 52, or

[0215] direct dyes in the presence of cationic amphotere, substantivepolymer, as described in EP-953 334, especially on page 2, line 39 topage 7, line 44, with direct dyes as described on page 8, line 54 topage 27, line 16, and polymers as described on page 27, line 17 to page30, line 14, or

[0216] direct dyes formulations with polymer thickener on the basis ofacrylic acid, as described in EP-970 685, especially on page 2, line 39to page 10, line 1, with direct dyes as described on page 10, line 7 topage 48, line 15, with polymers as described on page 48, line 17 to page49, line 28.

[0217] The coloring composition according to the invention in many casescomprises at least one surfactant. Suitable surfactants are anionic,zwitterionic, ampholytic, non-ionic and cationic surfactants. In manycases, however, it has proved advantageous to select the surfactantsfrom anionic, zwitterionic and non-ionic surfactants.

[0218] Anionic surfactants suitable for use in the coloring compositionsaccording to the invention include all anionic surface-active substancesthat are suitable for use on the human body. Such substances arecharacterised by an anionic group that imparts water solubility, forexample a carboxylate, sulfate, sulfonate or phosphate group, and alipophilic alkyl group having approximately from 10 to 22 carbon atoms.In addition, glycol or polyglycol ether groups, ester, ether and amidegroups and also hydroxy groups may be present in the molecule. Thefollowing are examples of suitable anionic surfactants, each in the formof sodium, potassium or ammonium salts or mono-, di- ortri-alkanolammonium salts having 2 or 3 carbon atoms in the alkanolgroup:

[0219] linear fatty acids having from 10 to 22 carbon atoms (soaps),

[0220] ether carboxylic acids of formula R—O—(CH₂—CH₂—O)_(x)—CH₂—COOH,in which R is a linear alkyl group having from 10 to 22 carbon atoms andx=0 or from 1 to 16,

[0221] acyl sarcosides having from 10 to 18 carbon atoms in the acylgroup,

[0222] acyl taurides having from 10 to 18 carbon atoms in the acylgroup,

[0223] acyl isothionates having from 10 to 18 carbon atoms in the acylgroup,

[0224] sulfosuccinic mono- and di-alkyl esters having from 8 to 18carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylesters having from 8 to 18 carbon atoms in the alkyl group and from 1 to6 oxyethyl groups,

[0225] linear alkane sulfonates having from 12 to 18 carbon atoms,

[0226] linear α-olefin sulfonates having from 12 to 18 carbon atoms,

[0227] α-sulfo fatty acid methyl esters of fatty acids having from 12 to18 carbon atoms,

[0228] alkyl sulfates and alkyl polyglycol ether sulfates of formulaR′—O(CH₂—CH₂—O)_(x)—SO₃H, in which R′ is a preferably linear alkyl grouphaving from 10 to 18 carbon atoms and x′=0 or from 1 to 12,

[0229] mixtures of surface-active hydroxysulfonates according to DE-A-3725 030, especially page 3, lines 40 to 55,

[0230] sulfated hydroxyalkylpolyethylene and/or hydroxyalkylenepropyleneglycol ethers according to DE-A-3 723 354, especially page 4, lines 42to 62,

[0231] sulfonates of unsaturated fatty acids having from 12 to 24 carbonatoms and from 1 to 6 double bonds according to DE-A-3 926 344,especially page 2, lines 36 to 54,

[0232] esters of tartaric acid and citric acid with alcohols which areaddition products of approximately from 2 to 15 molecules of ethyleneoxide and/or propylene oxide with fatty alcohols having from 8 to 22carbon atoms, or

[0233] anionic surfactants, as described in WO 00/10518, especially page45, line 11 to page 48, line 3.

[0234] Preferred anionic surfactants are alkyl sulfates, alkylpolyglycol ether sulfates and ether carboxylic acids having from 10 to18 carbon atoms in the alkyl group and up to 12 glycol ether groups inthe molecule, and also especially salts of saturated and especiallyunsaturated C₈-C₂₂carboxylic acids, such as oleic acid, stearic acid,isostearic acid and palmitic acid.

[0235] Surface-active compounds that carry at least one quaternaryammonium group and at least one —COO⁽⁻⁾ or —SO₃ ⁽⁻⁾ group in themolecule are termed zwitterionic surfactants. Zwitterionic surfactantsthat are especially suitable are the so-called betaines, such as theN-alkyl-N,N-dimethylammonium glycinates, for examplecocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyl-dimethylammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having from 8 to 18carbon atoms in the alkyl or acyl group and alsococoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferredzwitterionic surfactant is the fatty acid amide derivative known by theCTFA name cocoamidopropyl betaine.

[0236] Ampholytic surfactants are to be understood as meaningsurface-active compounds that, in addition to a C₈-C₁₈-alkyl or -acylgroup, contain at least one free amino group and at least one —COOH or—SO₃H group in the molecule and are capable of forming internal salts.Examples of suitable ampholytic surfactants include N-alkylglycines,N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl-glycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids, each having approximately from 8 to 18 carbon atoms in the alkylgroup. Ampholytic surfactants to which special preference is given areN-cocoalkyl-aminopropionate, cocoacylaminoethylaminopropionate andC₁₂-C₁₈acylsarcosine.

[0237] Non-ionic surfactants are described in WO 00/10519, especiallypage 45, line 11 to page 50, line 12.

[0238] Non-ionic surfactants contain as the hydrophilic group, forexample, a polyol group, a polyalkylene glycol ether group or acombination of polyol and polyglycol ether groups.

[0239] Such compounds are, for example:

[0240] addition products of from 2 to 30 mol of ethylene oxide and/orfrom 0 to 5 mol of propylene oxide with linear fatty alcohols havingfrom 8 to 22 carbon atoms, with fatty acids having from 12 to 22 carbonatoms and with alkylphenols having from 8 to 15 carbon atoms in thealkyl group,

[0241] C₁₂-C₂₂ fatty acid mono- and di-esters of addition products offrom 1 to 30 mol of ethylene oxide with glycerol,

[0242] C₈-C₂₂alkyl-mono- and -oligo-glycosides and ethoxylated analoguesthereof,

[0243] addition products of from 5 to 60 mol of ethylene oxide withcastor oil and hydrogenated castor oil,

[0244] addition products of ethylene oxide with sorbitan fatty acidesters,

[0245] addition products of ethylene oxide with fatty acidalkanolamides.

[0246] Examples of cationic surfactants that can be used in the coloringcompositions according to the invention are especially quaternaryammonium compounds. Preference is given to ammonium halides, such asalkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides andtrialkylmethylammonium chlorides, for example cetyltrimethylammoniumchloride, stearyltrimethylammonium chloride, distearyldimethy-lammoniumchloride, lauryidimethylammonium chloride, lauryidimethylbenzylammoniumchloride and tricetylmethylammonium chloride. Further cationicsurfactants that can be used in accordance with the invention arequatemised protein hydrolysates.

[0247] Also suitable in accordance with the invention are cationicsilicone oils, such as, for example, the commercially available productsQ2-7224 (manufacturer: Dow Corning; a stabilisedtrimethylsilylamodimethicone), Dow Corning 929 emulsion (comprising ahydroxylamino-modified silicone, which is also referred to asamodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067(manufacturer: Wacker) and also Abil®-Quat 3270 and 3272 (manufacturer:Th. Goldschmidt; diquatemary polydimethylsiloxanes, quatemium-80), orsilicones, as described in WO 00/12057, especially page 45, line 9 topage 55, line 2.

[0248] Alkylamidoamines, especially fatty acid amidoamines, such as thestearylamidopropyl-dimethylamine obtainable under the name Tego Amid®18, are distinguished not only by a good conditioning action but alsoespecially by their good biodegradability.

[0249] Quaternary ester compounds, so-called “esterquats”, such as themethyl hydroxyalkyl-dialkoyloxyalkylammonium methosulfates marketedunder the trademark Stepantex®, are also very readily biodegradable.

[0250] An example of a quaternary sugar derivative that can be used ascationic surfactant is the commercial product Glucquat® 100, accordingto CTFA nomenclature a “lauryl methyl gluceth-10 hydroxypropyl dimoniumchloride”.

[0251] The alkyl-group-containing compounds used as surfactants may besingle substances, but the use of natural raw materials of vegetable oranimal origin is generally preferred in the preparation of suchsubstances, with the result that the substance mixtures obtained havedifferent alkyl chain lengths according to the particular startingmaterial used.

[0252] The surfactants that are addition products of ethylene and/orpropylene oxide with fatty alcohols or derivatives of such additionproducts may either be products having a “normal” homologue distributionor products having a restricted homologue distribution. “Normal”homologue distribution is to be understood as meaning mixtures ofhomologues obtained in the reaction of fatty alcohol and alkylene oxideusing alkali metals, alkali metal hydroxides or alkali metal alcoholatesas catalysts. Restricted homologue distributions, on the other hand, areobtained when, for example, hydrotalcites, alkali metal salts of ethercarboxylic acids, alkali metal oxides, hydroxides or alcoholates areused as catalysts. The use of products having restricted homologuedistribution may be preferred.

[0253] Further preferred active ingredients of formulation according tothe present invention, adjuvants and additives are as follows:

[0254] non-ionic polymers, for example vinylpyrrolidone/vinyl acrylatecopolymers, polyvinyl-pyrrolidone and vinylpyrrolidone/vinyl acetatecopolymers and polysiloxanes,

[0255] cationic polymers, such as quaternised cellulose ethers,polysiloxanes having quaternary groups, dimethyldiallylammonium chloridepolymers, copolymers of dimethyidiallylammonium chloride and acrylicacid, as available commercially under the name Merquat® 280 and the useof which in hair coloring is described, for example, in DE-A-4 421 031,especially page 2, lines 20 to 49, or EP-A-953 334, especially page 27,line 17 to page 30, line 11, acrylamide/dimethyldiallylammonium chloridecopolymers, diethyl-sulfate-quatemised dimethylaminoethylmethacrylate/vinylpyrrolidone copolymers, vinylpyrrolidone/imidazoliniummethochloride copolymers,

[0256] quaternised polyvinyl alcohol,

[0257] zwitterionic and amphoteric polymers, such as, for example,acrylamido-propyl-trimethylammonium chloride/acrylate copolymers andoctylacrylamide/methyl methacrylate/tert-butylaminoethylmethacrylate/2-hydroxypropyl methacrylate copolymers,

[0258] anionic polymers, such as, for example, polyacrylic acids,crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers,vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobomyl acrylate copolymers, methyl vinyl ether/maleicanhydride copolymers and acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers,

[0259] thickeners, such as agar, guar gum, alginates, xanthan gum, gumarabic, karaya gum, locust bean flour, linseed gums, dextrans, cellulosederivatives, e.g. methyl cellulose, hydroxyalkyl cellulose andcarboxymethyl cellulose, starch fractions and derivatives, such amylose,amylopectin and dextrins, clays, e.g. bentonite or fully synthetichydrocolloids such as, for example, polyvinyl alcohol,

[0260] structuring agents, such as glucose and maleic acid,

[0261] hair-conditioning compounds, such as phospholipids, for examplesoya lecithin, egg lecithin, and cephalins, silicone oils, and alsoconditioning compounds, for example such as those described in DE-A-19729 080, especially page 2, lines 20 to 49, EP-A-834 303, especiallypage 2, line 18 to page 3, line 2, or EP-A-312 343, especially page 2,line 59 to page 3, line 11,

[0262] protein hydrolysates, especially elastin, collagen, keratin, milkprotein, soya protein and wheat protein hydrolysates, condensationproducts thereof with fatty acids and also quatemised proteinhydrolysates,

[0263] perfume oils, dimethyl isosorbitol and cyclodextrins,

[0264] solubilisers, such as ethanol, isopropanol, ethylene glycol,propylene glycol, glycerol and diethylene glycol,

[0265] anti-dandruff active ingredients, such as piroctones, olaminesand zinc Omadine,

[0266] further substances for adjusting the pH value,

[0267] active ingredients such as panthenol, pantothenic acid,allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extractsand vitamins,

[0268] cholesterol,

[0269] light stabilisers and UV absorbers, as described, for example, inEP-A-81 9 422, especially page 4, lines 34 to 37,

[0270] consistency regulators, such as sugar esters, polyol esters orpolyol alkyl ethers,

[0271] fats and waxes, such as spermaceti, beeswax, montan wax,paraffins, fatty alcohols and fatty acid esters,

[0272] fatty alkanolamides,

[0273] polyethylene glycols and polypropylene glycols having a molecularweight of from 150 to 50 000, for example such as those described inEP-A-801 942, especially page 3, lines 44 to 55,

[0274] complexing agents, such as EDTA, NTA and phosphonic acids,

[0275] swelling and penetration substances, such as polyols and polyolethers, as listed extensively, for example, in EP-A-962 219, especiallypage 27, lines 18 to 38, for example glycerol, propylene glycol,propylene glycol monoethyl ether, butyl glycol, benzyl alcohol,carbonates, hydrogen carbonates, guanidines, ureas and also primary,secondary and tertiary phosphates, imidazoles, tannins, pyrrole,

[0276] opacifiers, such as latex,

[0277] pearlising agents, such as ethylene glycol mono- and di-stearate,

[0278] propellants, such as propane-butane mixtures, N₂O, dimethylether, CO₂ and air, and also

[0279] antioxidants,

[0280] polyols or polyethers, as described in EP-A-962 219, especiallypage 27, lines 14 to 38,

[0281] thickening polymers, as described in EP-A-970 684, especiallypage 48, line 16 to page 51, line 4,

[0282] sugar-containing polymers, as described in EP-A-970 687,especially page 28, line 17 to page 29, line 23,

[0283] quaternary ammonium salts, as described in WO 00/10517,especially page 44, line 16 to page 46, line 23.

[0284] In the context of the present invention, oxidizing agents areunderstood to be any oxidizing agent customarily used for oxidative haircoloring, for example dilute hydrogen peroxide solutions, hydrogenperoxide emulsions or hydrogen peroxide gels, alkaline earth metalperoxides, organic peroxides, such as urea peroxides, melamineperoxides, or alkalimetalbromat fixations are also applicable if ashading powder on the basis of semi-permanent, direct hair dyes is used.

[0285] Preferred oxidizing agent is hydrogen peroxide, preferred inabout 2 to 30% by weight, more preferred in 3 to 20% by weight, and mostpreferred in 6 to 12% by weight of the total weight of a waterycomposition such as a solution, dispersion, a gel or emulsion.

[0286] The watery composition can comprise all customary components,which are used for the different applications of oxidizing agentcompositions as described in K. Schrader, “Grundlagen und Rezepturen derKosmetika”, 2. Aufl. (1989), page 832-840.

[0287] Further preferred oxidizing agents are

[0288] oxidizing agents to achieve lightened coloration, as described inWO 97/20545, especially page 9, lines 5 to 9,

[0289] oxidizing agents in the form of permanent-wave fixing solution,as described in DE-A-19 713 698 , especially page 4, lines 52 to 55, andlines 60 and 61 or EP-A-1 062 940, especially page 6, lines 41 to 47,(and in the equivalent WO 99/40895).

[0290] An oxidizing agents may be present in the coloring compositionsaccording to the invention preferably in an amount of from 0.01% to 6%,especially from 0.01% to 1%, based on the total dyeing composition.

[0291] Preferred catalysts are metal ions, such as for example Zn²⁺,Cu²⁺, Fe²⁺, Fe³⁺, Mn²+, Mn⁴⁺, Li⁺, Mg²⁺, Ca²⁺ and Al³⁺, preferably Zn²⁺,Cu²⁺ and Mn²⁺.

[0292] The metal ions are applicable in any physiological suitable saltsform. Preferred salts are acetate, sulfate, halogenide, lactate andtartrate.

[0293] Alkalimetalsulfits, such as sodium-, potassium-, lithium-sulfite,Alkalimetaldisulfits, such as sodium-, potassium-, lithium-disulfite,ascorbic acid, tert.-Butylhydrochinon and Ammoniumthiolactat.

[0294] In general, the coloration with an oxidative agent is conductedin the presence of a base. Bases are for example ammonia, alkali metalcarbonates, earth metal carbonates, alkanol amines, such as for examplemono-, di- or triethanolamine, alkali metal hydroxides, earth metalhydroxides, compounds of the formula

[0295] wherein,

[0296] R is a propyl residue, which substituted with OH or C₁-C₄-alkyl,

[0297] R₃, R₄, R₅ and R₆ are independently or dependently from eachother hydrogen, C₁-C₄-alkyl or hydroxy-(C₁-C₄)-alkyl.

[0298] Alkali metal is for example sodium, potassium or lithium.

[0299] Earth metal is for example magnesium or calcium.

[0300] Acids are inorganic or organic acids, such as hydrochloride,tartrat acid, citric acid, ascorbic acid and phosphor acid.

[0301] The use of UV absorbers can effectively protect natural and dyedhair from the damaging rays of the sun and increase the wash fastness ofdyed hair.

[0302] Preferred UV absorbers the coloring compositions according to theinvention are:

[0303] cationic benzotriazole UV absorbers as for example described inWO 01/36396 especially on page 1, line 20 to page 2, line 24, andpreferred on page 3 to 5, and on pages 26 to 37, or

[0304] cationic benzotriazole UV in combination with antioxidants asdescribed in WO 01/36396, especially on page 11, line 14 to page 18, or

[0305] UV absorbers in combination with antioxidants as described inU.S. Pat. No. 5,922,310, especially in column 2, lines 1 to 3,

[0306] UV absorbers in combination with antioxidants as described inU.S. Pat. No. 4,786,493, especially in column 1, 42 to column 2, line 7,and preferred in column 3, 43 to column 5, line 20, or

[0307] combination of UV absorbers as described in U.S. Pat. No.5,830,441, especially in column 4, lines 53 to 56, or

[0308] combination of UV absorbers as described in WO 01/36396,especially on page 11, lines 9 to 13, or

[0309] triazine derivatives provide effective UV protection as describedin WO 98/22447, especially on page 1, line 23 to page 2, line 4, andpreferred on page 2, line 11 to page 3, line 15 and most preferred onpages 6 to 7, and 12 to 16, or

[0310] combination of the cosmetic formulations as described in WO98/22447 with one or more than one further UV filter as described in thefollowing patents:

[0311] (Abbreviations T: table, R: row, Comp: compound, Ex: compound(s)of patent example, p=page; pp=pages) EP 895776 Comp. in Rows 48-58, p 3;R 25 + 33, p 5 WO 9220690 Polymeric comp in Examples 3-6 EP 1000950Comp. in Table 1, pp 18-21 EP 1060734 T 1-3, pp 11-14 EP 1059082 Ex 1; T1, pp 9-11 EP 1008586 Ex 1-3, pp 13-15 EP 1005855 T 3, p 13 EP 1129695Ex 1-7, pp 13-14 EP 967200 Ex 2; T 3-5, pp 17-20 EP 945125 T 3 a + b, pp14-15 EP 924246 T 2, p 9 EP 911020 T 2, p 11-12 EP 916335 T 2-4, pp19-41 EP 852137 T 2, pp 41-46 EP 858318 T 1, p 6 EP 826361 T 1, pp 5-6EP 503338 T 1, pp 9-10 WO 9301164 T 1 + 2, pp 13-22 EP 823418 Ex 1-4, pp7-8 WO 9714680 Ex 1-3, p 10 EP 1027883 Compound VII, p 3 EP 832641 Ex5 + 6 p 7; t 2, p 8 U.S. Pat. No. 5338539 Ex 1-9, pp 3 + 4 EP 517103 Ex3, 4, 9, 10 pp 6-7 EP 1123934 T 3, p 10 EP 1027883 Comp I-VI, p 3 EP969004 Ex 5, T 1, pp 6-8 U.S. Pat. No. 5801244 Ex 1-5, pp 6-7 EP 832642Ex 22,T 3 pp, 10-15; T 4, p 16 U.S. Pat. No. 5346691 Ex 40, p 7; T 5, p8 (EP 570838) EP 517104 Ex 1,T 1, pp 4-5; Ex 8, T 2, pp 6-8 WO 200149686Ex 1-5, pp 16-21 EP 944624 Ex 1 + 2, pp 13-15 EP 933376 Ex 1-15, pp10-21 EP 863145 Ex 1-11, pp 12-18 EP 780382 Ex 1-11, pp 5-7 EP 626950All examples EP 1081140 Ex 1-9, pp 11-16 WO 9217461 Ex 1-22, pp 10-20 WO0168047 Tables on pp 85-96 EP 613893 Ex 1-5 + 15, T 1, pp 6-8 EP 1064922Compounds 1-34, pp 6-14 EP 1028120 Ex 1-5, pp 5-13 EP 1008593 Ex 1-8, pp4-5 EP 669323 Ex 1-3, p 5 EP 11087124,5-Dimorpholino-3-hydroxypyridazine JP 2000319629 CAS Regno.80142-49-0, 137215-83-9, 307947-82-6 EP 420707 B1 Ex 3, p 13(80142-49-0) U.S. Pat. No. 5635343 All examples EP 1167358 All examples

[0312] A preferred embodiment of the present invention concerns thecombination of a compound of formula (1) with UV absorbers.

[0313] Preferred UV absorbers are described in WO 98/22447.

[0314] Preferred cosmetic formulations contain a combination of acompound of formula (1) with UV absorbers and one or more than onefurther UV protective of the following substance classes:

[0315] p-aminobenzoic acid derivatives, for example4-dimethylaminobenzoic acid 2-ethylhexyl ester;

[0316] salicylic acid derivatives, for example salicylic acid2-ethylhexyl ester;

[0317] benzophenone derivatives, for example2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative;

[0318] dibenzoylmethane derivatives, for example1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-propane-1,3-dione;

[0319] diphenylacrylates, for example 2-ethylhexyl2-cyano-3,3-diphenylacrylate, and 3-(benzofuranyl) 2-cyanoacrylate;

[0320] 3-imidazol-4-ylacrylic acid and esters;

[0321] benzofuran derivatives, especially 2-(p-aminophenyl)benzofuranderivatives, described in EP-A-582 189, U.S. Pat. No. 5,338,539, U.S.Pat. No. 5,518,713 and EP-A-613 893;

[0322] polymeric UV absorbers, for example the benzylidene malonatederivatives described in EP-A-709 080;

[0323] cinnamic acid derivatives, for example the 4-methoxycinnamic acid2-ethylhexyl ester and isoamyl ester or cinnamic acid derivativesdescribed in U.S. Pat. No. 5,601,811 and WO 97/00851; camphorderivatives, for example 3-(4′-methyl)benzylidene-boman-2-one,3-benzylidene-boman-2-one, N-[2(and4)-2-oxybom-3-ylidene-methyl)-benzyl]acrylamide polymer,3-(4′-trimethylammonium)-benzylidene-boman-2-one methyl sulfate,3,3′-(1,4-phenylenedimethine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonicacid) and salts, 3-(4′-sulfo)benzylidene-boman-2-one and salts;camphorbenzalkonium methosulfate;

[0324] hydroxyphenyltriazine compounds, for example2-(4′-methoxyphenyl)-4,6-bis(2′-hydroxy-4′-n-octyloxyphenyl)-1,3,5-triazine;2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-[4-(2-methoxyethyl-carboxyl)-phenylamino]-1,3,5-triazine;2,4-bis{[4-(tris(trimethylsilyloxy-silylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(2″-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethyltrsilyl-2″-methyl-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-[4-ethylcarboxy)-phenylamino]-1,3,5-triazine;

[0325] benzotriazole compounds, for example2,2′-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol;

[0326] trianilino-s-triazine derivatives, for example2,4,6-trianiline-(p-carbo-2′-ethyl-1′-oxy)-1,3,5-triazine and the UVabsorbers disclosed in U.S. Pat. No. 5,332,568, EP-A-517 104, EP-A-507691, WO 93/17002 and EP-A-570 838;

[0327] 2-phenylbenzimidazole-5-sulfonic acid and salts thereof;

[0328] methyl o-aminobenzoates;

[0329] physical sunscreens coated or not as titanium dioxide, zincoxide, iron oxides, mica, MnO, Fe₂O₃, Ce₂O₃, Al₂O₃, ZrO₂. (surfacecoatings: polymethylmethacrylate, methicone (methylhydrogenpolysiloxaneCAS 9004-73-3), dimethicone, isopropyl titanium triisostearate (CAS61417-49-0), metal soaps as magnesium stearate (CAS 4086-70-8),perfluoroalcohol phosphate as C9-15 fluoroalcohol phosphate (CAS74499-44-8; JP 5-86984, JP 4-330007)). The primary particle size is anaverage of 15 nm-35 nm and the particle size in dispersion is in therange of 100 nm-300 nm.

[0330] aminohydroxy-benzophenone derivatives disclosed in DE 10011317,EP 1133980 and EP 1046391

[0331] phenyl-benzimidazole derivatives as disclosed in EP 1167358.

[0332] The UV absorbers described in “Sunscreens”, Eds. N. J. Lowe, N.A. Shaath, Marcel Dekker, Inc., New York and Basle or in Cosmetics &Toiletries (107), 50ff (1992) also can be used as additional UVprotective substances.

[0333] Synergistic effects are observed when UV absorbers are used incombination with antioxidants. Examples of antioxidants that can be usedare listened in WO 01/36396 (pages 11-18), U.S. Pat. No. 5,922,310 andU.S. Pat. No. 4,786,493.

[0334] Further preferred UV absorbers used in addition to the unchargedand cationic benzotriazole UV absorbers in the formulations withoutlimitation to those listed in the following are benzophenone-typesubstances such as benzophenone-1, benzophenone-2, benzophenone-3,benzophenone-4, benzophenone-5 (sodium salt) or benzotriazol-typesubstances such as benzenesulfonic acid,3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-, monosodium salt;2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl-phenol;2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-phenol, branched and linear.

[0335] Typical ingredients in the oil phase of emulsions (water in oil,oil in water or triple emulsion) or used in hair oils can be chosen fromthe following substance groups without limiting the kind of lipophilicingredients to those substances:

[0336] Suitable cosmetic preparations may contain usually from 0.05 to40% by weight, preferably from 0.1 to 20% by weight, based on the totalweight of the composition, of one or more UV absorbers.

[0337] Preferred are the cosmetic preparations contain at least onetriazine derivative UV absorber, for example, from 0.1 to 40% by weight,preferably from 0.1 to 20% by weight and especially from 0.5 to 10% byweight, based on the total weight of the composition, and the cosmeticpreparations contain at least one cationic benzotriazole from 0.05-20%by weight, preferred from 0.1-20% by weight, based on the total weightof the composition. Typical cosmetic formulations containing unchargedand/or cationic benzotriazoles and/or antioxidants alone or incombinations are rinse-off products (e.g. shampoos, hair rinses,conditioners etc.),

[0338] Suitable cosmetic formulations are:

[0339] cosmetic hair-treatment preparations, e.g. hair-washingpreparations in the form of shampoos and conditioners, hair-carepreparations, e.g. pre-treatment preparations or leave-on products suchas sprays, creams, gels, lotions, mousses and oils, or

[0340] hair tonics, styling creams, styling gels, pomades, hair rinses,treatment packs, intensive hair treatments, hair-structuringpreparations, e.g. hair-waving preparations for permanent waves (hotwave, mild wave, cold wave), hair-straightening preparations, liquidhair-setting preparations, hair foams, hairsprays, bleachingpreparations, e.g. hydrogen peroxide solutions, lightening shampoos,bleaching creams, bleaching powders, bleaching pastes or oils,temporary, semi-permanent or permanent hair colorants, preparationscontaining self-oxidizing dyes, or natural hair colorants, such as hennaor camomile.

[0341] The final formulations listed may exist in a wide variety ofpresentation forms, for example:

[0342] in the form of liquid preparations as a W/O, O/W, OM/O, W/O/w orPIT emulsion and all kinds of microemulsions,

[0343] in the form of a gel,

[0344] in the form of an oil, a cream, milk or lotion,

[0345] in the form of a powder, a lacquer, a tablet or make-up,

[0346] in the form of a stick,

[0347] in the form of a spray (spray with propellant gas or pump-actionspray) or an aerosol,

[0348] in the form of a foam, or

[0349] in the form of a paste.

[0350] Of special importance as cosmetic preparations for the hair arethe above-mentioned preparations for hair treatment, especiallyhair-washing preparations in the form of shampoos, hair conditioners,hair-care preparations, e.g. pre-treatment preparations, hair tonics,styling creams, styling gels, pomades, hair rinses, treatment packs,intensive hair treatments, hair-straightening preparations, liquidhair-setting preparations, hair foams and hairsprays. Of specialinterest are hair-washing preparations in the form of shampoos.

[0351] A shampoo has, for example, the following composition: from 0.01to 5% by weight of a UV absorber according to the invention, 12.0% byweight of sodium laureth-2-sulfate, 4.0% by weight of cocoamidopropylbetaine, 3.0% by weight of sodium chloride, and water ad 100%.

[0352] A further embodiment of the present invention concerns micronisedUV absorbers, for example:

[0353] wet-grinding with a hard grinding medium, for example zirconiumsilicate and a protective surfactant or a protective polymer in water orin a suitable organic solvent;

[0354] spray-drying from a suitable solvent, for example aqueoussuspensions or suspensions containing organic solvents, or truesolutions in water, ethanol, dichloroethane, toluene orN-methylpyrrolidone etc.;

[0355] by the expansion according to the RESS process (Rapid Expansionof Supercritical Solutions) of supercritical fluids (e.g. CO₂) in whichthe UV filter or filters is/are dissolved, or the expansion of fluidcarbon dioxide together with a solution of one or more UV filters in asuitable organic solvent;

[0356] by reprecipitation from suitable solvents, includingsupercritical fluids (GASR process=Gas Anti-SolventRecrystallisation/PCA process=Precipitation with CompressedAnti-solvents).

[0357] As grinding apparatus for the preparation of the micronisedorganic UV absorbers there may be used, for example, a jet mill, ballmill, vibratory mill or hammer mill, preferably a high-speed mixingmill. The grinding is preferably carried out with a grinding aid, forexample an alkylated vinylpyrrolidone polymer, a vinylpyrrolidone/vinylacetate copolymer, an acyl glutamate, an alkyl polyglucoside,ceteareth-25 or a phospholipid.

[0358] The micronised UV absorbers so obtained usually have an averageparticle size that is from 0.02 to 2 μm, preferably from 0.05 to 1.5 μm,and more especially from 0.1 to 1.0 μm.

[0359] The UV absorbers can also be used dry in powder form. For thatpurpose the UV absorbers are subjected to known grinding methods, suchas vacuum atomization, countercurrent spray-drying etc. Such powdershave a particle size of from 0.1 μm to 2μm. To avoid the occurrence ofagglomeration, the UV absorbers can be coated with a surface-activecompound prior to the pulverisation process, for example with ananionic, non-ionic or amphoteric surfactant, e.g. a phospholipid or aknown polymer, such as PVP, or an acrylate. The coloring compositionsaccording to the invention may further comprise antimicrobial agents.

[0360] Preferred antimicrobial preservatives and antimicrobial activesused in formulations (in most cases the INCI name of the antimicrobialsubstances is mentioned):

[0361] formaldehyde and paraformaldehyde, hydroxy biphenyls and itssalts such as ortho-phenylphenol, zinc pyrithion, chlorobutanol, hydroxybenzoic acids and their salts and esters such as methyl paraben, ethylparaben, propyl paraben, butyl paraben, dibromo hexamidine and its saltsincluding isothionate (4,4′-hexamethylenedioxy-bis(3-bromo-benzamidine)and 4,4′-hexamethylenedioxy-bis(3-bromo-benzamidinium2-hydroxyethanesulfonate), mercury, (aceto-O)phenyl (especially phenylmercuric acetate) and Mercurate(2-),(orthoborate(3-)-O)phenyl,dihydrogene (especially phenyl mercuric borate),1,3-bis(2-ethylhexyl)-hexahydro-5-methyl-5-pyrimidine (Hexetidin),5-bromo-5-nitro-1,3-dioxan, 2-bromo-2-nitro-1,3-propandiol,2,4-dichlorobenzyl alcohol, 3,4,4′ trichlorocarbanilide(Trichlorcarban), p-chloro-m-cresol, 2,4,4′-trichloro 2-hydroxydiphenylether (triclosan), 4,4′-dichloro 2-hydroxy diphenylether,4-chloro-3,5-dimethylphenol (Chloroxylenol), imidazolidinyl urea,poly-(hexamethylene biguanide) hydrochloride, 2-phenoxy ethanol(phenoxyethanol), hexamethylene tetramine (Methenamine),1-(3-chloroallyl)-3,5,7-triaza-1-azonia-adamantanchloride (Quaternium15), 1-(4-chlorophenyoxy)-1-(1-imidazolyl)3,3-dimethyl-2-butanone(Climbazole), 1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione(DMDM hydantoin), benzyl alcohol, 1,2-dibromo-2,4-dicyano butane, 2,2′methylene-bis(6-bromo-4-chloro phenol) (bromochlorophene),methylchloroisothiazolone, methylisothiazolone, octylisothiazolone,benzylisothiazolone, 2-benzyl-4-chlorophenol (Chlorophenone),chloracetamide, chlorhexidine, chlorhexidine acetate, chlorhexidinegluconate, chlorhexidine hydrochloride, 1-phenoxy-propane-2-ol(phenoxyisopropanol), 4,4-dimethyl-1,3-oxazolidine (dimethyloxazolidine), diazolidinyl urea, 4,4′-hexamethylenedioxybisbenzamidineand 4,4′-hexamethylenedioxybis(benzamidinium-2-hydroxyethanesulfonate),glutaraldehyde (1,5-pentanedial), 7-ethylbicyclooxazolidine,3-(4-chlorophenoxy)-1,2-propandiol (chlorophenesin),phenylmethoxymethanol and ((phenylmethoxy)methoxy)-methanol(benzylhemiformal), N-alkyl(C12-C22)trimethyl ammoniumbromide and-chloride (cetrimonium bromide, cetrimonium chloride),benzyl-dimethyl-(4-(2-(4-(1,1,3,3-tetramethylbutyl)-phenoxy)-ethoxy)-ethyl)-ammoniumchloride(benzethonium chloride), Alkyl-(C8-C18)-dimethyl-benzylammoniumchloride, -bromide and saccharinate (benzalkonium chloride, benzalkoniumbromide, benzalkonium saccharinate), benzoic acid and its salts andesters, propionic acid and its salts, salicylic acid and its salt,sorbic acid and its salts, sodium iodiate, inorganic sulfites andbisulfites such as sodium sulfite, dehydroacetic acid, formic acid,mercu rate(1-ethyl)2-mercaptobenzoate(2-)—O,S—,hydrogene (Thiomersal orThiomerosal), 10-undecylenic acid and its salts, octopirox (piroctoneolamine), sodium hydroxy methyl-aminoacetate (sodiumhydroxymethylglycinate), 3-iodo-2-propynyl butylcarbamate,10-undecylenic acid, sulfur.

[0362] Combinations with natural antimicrobials or chemically modifiednatural substances with antimicrobial activities such as chitosans andchitosan derivatives, famesol, plant extracts such as clove oil, bluecypres oil etc. can be also used.

[0363] For use on human hair, the dyeing compositions can usually beincorporated into an aqueous cosmetic carrier. Suitable aqueous cosmeticcarriers include, for example, creams, sprays, emulsions, gels, powdersand also surfactant-containing foaming solutions, e.g. shampoos or otherpreparations, that are suitable for use on keratin-containing fibers.Such forms of use are described in detail in Research Disclosure 42448(August 1999). If necessary, it is also possible to incorporate thedyeing compositions into anhydrous carriers, as described, for example,in U.S. Pat. No. 3,369,970, especially column 1, line 70 to column 3,line 55. The dyeing compositions according to the invention are alsoexcellently suitable for the coloring method described in DE-A-3 829 870using a coloring comb or a coloring brush.

[0364] Further carriers for dying compositions are for example describedin “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel DekkerInc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of HairCare, chapter 7, pages 248-250, especially on page 243, line 1 to page244, line 12.

[0365] Suitable formulations of cationic dyes, which can be used in thecoloring compositions according to the invention, are described forexample in

[0366] in WO 95/01772, especially on page 11, line 29 to page 12, line7, or

[0367] in WO 01/66646, especially on page 7, line 1 to page 22, andpreferred from page 16, line 20 to page 22, or

[0368] direct dyes as described in DE-A-19 713 698, especially page 3,line 51 to page 4, line 29 and page 4, line 65 to page 5, line 60, or

[0369] direct dyes and oxidizing agent as described in WO 97/20545,especially on page 9, line 1 to page 11, line 4, in particular on page11, line 6 to page 13, line 19.

[0370] Preferred formulations of cationic dyes with other dyes, whichcan be used in the coloring compositions according to the invention,are:

[0371] combinations of Pyrazolo-[1,5-a]-pyrimidines with at least onecationic dye as described in EP 998,908, especially on page 47, line 3to page 49, line 26, and preferred on page 51, line 4 to page 52, line5, or

[0372] combinations of cationic dyes as described in FR-2788432,especially on page 53, line 1 to page 63, line 23, especially acombination of cationic dyes with Arianors in FR-2788432, especially onpages 51 to 52, or especially a combination with at least one BasicBrown 17, Basic brown 16, Basic Red 76 and Basic Red 118, and/or atleast one Basic Yellow 57, and/or at least one Basic Blue 99, or

[0373] combinations of direct dyes and/or an oxidation dye and oxidizingagents in the form of permanent-wave fixing solution, especially withdirect dyes as described in DE-A-19 713 698, especially page 4, line 65to page 35, line 59, or

[0374] combinations of cationic dyes and an oxidation dye of thedeveloper compound type and oxidizing agents as described in EP 850 638,especially on page 2, lines 3 to 12 and line 30 to page 14, and page 28,line 35 to page 30, line 20, preferred on page 30, line 25 to page 32,line 30, or

[0375] ready-to-use dyeing compositions and multicompartment device fordyeing keratin fibers comprising combinations of an extemporaneousmixture of a composition (A) containing one or more oxidation dyeprecursors and optionally one or more couplers, and of a composition(B), in powder form, containing one or more direct dye, preferablycationic, optionally dispersed in an organic pulvenmlent excipientand/or a mineral pulverulent excipient, and a composition (C) containingone or more oxidizing agent as described in U.S. Pat. No. 6,190,421,especially in column 2, line 20 to line 31 in column 7, line 15 tocolumn 8, line 43, and preferably in column 8, line 55 to column 9, line56, and preferably with direct dyes as described in column 5, line 30 tocolumn 7, line 14, or

[0376] a ready-to-use composition comprising, at least one oxidationbase, at least one cationic direct dye and at least one enzyme of2-electron oxidoreductase type in the presence of at least one donor forthe said enzyme as described in U.S. Pat. No. 6,228,129, especially incolumn 2, line 16 to column 25, line 55, and a multi-compartment dyeingdevice as described in column 26, lines 13 to 24, especially in column26, line 26 to column 27, line 9, or

[0377] a ready-to-use composition comprising compositions of at leastone direct cationic dye and at least one nitrated benzene dye asdescribed in WO 99/20235 especially on page 1, line 25 to page 8, line5, and on page 30, line 17 to page 34 line 25, with cationic direct dyesas described on page 8, line 12 to page 25 line 6, and amulti-compartment dyeing device as described on page 35, lines 21 to 27,especially on page 36, line 1 to page 37, or

[0378] a ready-to-use composition or a multi-compartment dyeing devicecomprising compositions of at least one direct cationic dye and at leastone autooxidisable oxidation dye, especially benzene, indol and indolinederivatives as described in WO 99/20234, especially on page 26, line 5to page 32, line 18, or

[0379] oxidation dyeing compositions of at least one direct dye and atleast one meta-Aminophenol derivative and at least one developercompound and an oxidizing agent as described in EP 850 636, especiallyon page 18, line 1 to page 22, line 11, or

[0380] oxidation dyeing compositions of at least one direct dye and atleast one developer compound selected from the group ofpara-Phenylenediamine derivatives and Bis-Phenylalkylenediamine and, andat least one coupler compound selected from the group of meta-Diphenolsand an oxidizing agent, as described in EP-A-850 637, especially on page19, line 24 to page 22, line 57,

[0381] cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives,as described in EP 998 908, especially on page 47, line 25 to page 50,line 29, or

[0382] oxidative dye precursors (unsaturated aldehyde and couplercompounds), as described in German Patent Application 197 172 24,especially on page 3, line 36 to page 9 line 64.

[0383] Cationic dyes, especially compound of formula (1) may be presentin the coloring compositions according to the invention preferably in anamount of from 0.001% to 5%, especially from 0.01% to 1%, based on thetotal dyeing composition.

[0384] The pH value of the ready-to-use dyeing preparations is usuallyfrom 2 to 11, preferably from 5 to 10.

[0385] The constituents of the aqueous carrier are used in the coloringcompositions to the invention in the amounts customary for that purpose;for example emulsifiers may be used in concentrations of from 0.5 to 30%by weight and thickeners in concentrations of from 0.1 to 25% by weightof the total dyeing composition.

[0386] If direct dyes, especially of compound of formula (1) are usedtogether with oxidation dyes and/or the addition salts thereof with anacid, they may be stored separately or together.

[0387] It is preferred to store the oxidation dyes and direct dyes,which are not stable to reduction, separately.

[0388] They may be stored in a liquid to paste-like preparation (aqueousor non-aqueous) or in the form of a dry powder.

[0389] When the dyes and adjuvants are stored together in a liquidpreparation, the preparation should be substantially anhydrous in orderto reduce reaction of the compounds.

[0390] When they are stored separately, the reactive components areintimately mixed with one another only immediately before use. In thecase of dry storage, before use a defined amount of hot (from 50 to 80C)water is usually added and a homogeneous mixture prepared.

[0391] One preferred method of applying direct dyes containingformulations on hair is by using a multi-compartment dyeing device or“kit” or any other multi-compartment packaging system, as described forexample in WO 97/20545 on page 4, line 19 to line 27.

[0392] The coloring compositions according to the invention may combinedwith a suitable ready-to-use composition for the oxidation dyeing ofkeratin fibers, in particular human keratin, comprising an oxidizingagent, at least one direct dye, especially compound of formula (1) andat least one oxidation dye precursor, as described in U.S. Pat. No.6,190,421, in column 1, line 65 to column 3, line 65, especially incolumn 10, line 62 to column 12, line 65.

[0393] Preferably, such a ready-to-use composition is prepared accordingto a first preferred embodiment by a process which comprises apreliminary step which involves separately storing, on the one hand, acomposition (A) comprising, in a medium which is suitable for dyeing, atleast one developer compound, especially selected frompara-phenylenediamines and bis(phenyl)alkylenediamines, and theacid-addition salts thereof, at least one coupler, especially selectedfrom meta-phenylenediamines and the acid-addition salts thereof, and atleast one cationic direct dye, especially compound of formula (I), onthe other hand, a composition (B) containing, in a medium which issuitable for dyeing, at least one oxidizing agent and mixing themtogether at the time of use before applying this mixture to the keratinfibers.

[0394] According to a second preferred embodiment for the preparation ofthe ready-to-use dye composition, the process includes a preliminarystep which involves separately storing, on the one hand, a composition(A) comprising, in a medium which is suitable for dyeing, at least onedeveloper compound, especially selected from para-phenylenediamines andbis(phenyl)alkylenediamines, and the acid-addition salts thereof, atleast one coupler compound, especially selected frommeta-phenylenediamines and the acid-addition salts thereof; on the otherhand, a composition (A′) comprising, in a medium which is suitable fordyeing, at least one cationic direct dye, especially compound of formula(I), and, lastly, a composition (B) containing, in a medium which issuitable for dyeing, at least one oxidizing agent as defined above, andmixing them together at the time of use before applying this mixture tothe keratin fibers.

[0395] The composition (A′) used according to this second variant of theprocess in accordance with the invention can optionally be in powderform, the cationic direct dye(s) in accordance with the invention itself(themselves) constituting, in this case, all of the said composition(A′) or optionally being dispersed in an organic and/or inorganicpulverulent excipient.

[0396] When it is present in the composition A′, the organic excipientcan be of synthetic or plant origin and is selected in particular fromcrosslinked and non-crosslinked synthetic polymers, polysaccharides suchas celluloses and modified or unmodified starches, as well as naturalproducts containing them such as sawdust and plant gums (guar gum, carobgum, xanthan gum, etc.).

[0397] When it is present in the composition (A′), the inorganicexcipient can contain metal oxides such as titanium oxides, aluminiumoxides, kaolin, talc, silicates, mica and silicas.

[0398] An very suitable excipient in the coloring compositions accordingto the invention is sawdust. The powdered composition (A′) can alsocontain binders or coating products in an amount, which preferably doesnot exceed approximately 3% by weight relative to the total weight ofthe said composition (A′).

[0399] These binders are preferably selected from oils and liquid fattysubstances of inorganic, synthetic, animal or plant origin.

[0400] The composition (A′) may optionally also contain other adjuvants,in powdered form, in particular surfactants of any kind, hairconditioners such as, for example, cationic polymers, etc.

[0401] Another subject of the invention is a multi-compartment dyeingdevice or “kit” or any other multi-compartment packaging system, asdescribed for example in U.S. Pat. No. 6,228,129, especially in column26, lines 13 to 24, especially in column 26, line 26 to column 27, line9, or. A first compartment which contains the composition (A) as definedabove, an optional second compartment contains the composition (A′) asdefined above, when it is present, and a third compartment contains theoxidizing composition (B) as defined above. These devices can beequipped with means which allow the desired mixture to be applied to thehair, such as the devices described in French patent FR-2,586,913, thedisclosure of which is specifically incorporated by reference herein.

[0402] An oxidizing agent, which may be added to the coloringcompositions according to the invention containing composition,comprises an oxidizing agent and a base.

[0403] Further, this composition comprises for this oxidizing agentcontaining composition customary adjuvant and additives.

[0404] The formulations are for example a solution, especially athickened watery or watery alcoholic solution, a cream, foam, a gel, apowder or an emulsion. In general, preference is given to a creamformulation, a gel formulation or a foam formulation, and especially afoam formulation.

[0405] But, if stability- or solubility-problems arise it may ofadvantage to use powder formulation as for example described in DE 19713 698, page 2, line 26 to 54 and page 3, line 51 to page 4, line 25,and page 4, line 41 to page 5 line 59.

[0406] The oxidizing agent (calculated as hydrogen peroxide) is presentin this composition in 0.5 to 12% by weight, in particular from 1 to 6%by weight based on the totals weight of the oxidizing agent containingcomposition.

[0407] The pH-value of the oxidizing agent containing composition isusually about 2 to 7, and in particular about 3 to 6.

[0408] An oxidizing agent free composition, which may be added to thecoloring compositions according to the invention, comprises a developercompound and a coupler compound and a reduction agent, or

[0409] a developer compound or/and optionally a reduction agent, or

[0410] a coupler compound and a reduction agent.

[0411] Further, an oxidizing agent free composition may additionallycomprise a direct dye as for example described in German PatentApplication 199 59 479, column 3, line 12 to line 16.

[0412] Additionally, the oxidizing agent free composition usuallycomprises customary adjuvant and additives. Preferred are those, whichare described in German Patent Application, in column 3, line 17 to line41.

[0413] The pH-value of the oxidizing agent free composition is usuallyabout 3 to 11, and in particular about 5 to 10, and most particularabout 9 to 10.

[0414] For adjusting the pH-value organic or inorganic acids, as forexample described in German Patent Application 199 59 479, column 3,line 46 to line 53 are suitable.

[0415] The coloring compositions according to the invention may also becombined with hair dye compositions comprising an acid dye. Hair dyecompositions comprising an acid dye are known. For example, they aredescribed in “Dermatology”, edited by Ch. Culnan, H. Maibach, VeragMarcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, TheScience of Hair Care, chapter 7, pages 248-250, especially on page 253and 254.

[0416] The hair dye compositions comprising an acid dye have a pH of2-6, preferably 2-5, more preferably 2.5-4.0. If the pH is too low, theresulting composition may roughen the hair, scalp and hand skin due toan acid component in some cases. If the pH is too high, the penetrationaccelerating effect on the acid dye is lowered.

[0417] A compound of formula (1) according to the present invention mayalso readily be used in combination with other dyes and/or adjuvantsused in the coloring of hair, for example

[0418] acid dye and an alkylene carbonate, as described in U.S. Pat. No.6,248,314, especially in examples 1 and 2, or

[0419] acid hair dye compositions comprise various kinds of organicsolvents represented by benzyl alcohol as a penetrant solvent have goodpenetrability into hair, as described in Japanese Patent ApplicationLaid-Open Nos. 210023/1986 and 101841/1995, or

[0420] acid hair dye compositions with a water-soluble polymer or thelike to prevent the drooping of the hair dye composition, as describedfor example in Japanese Patent Application Laid-Open Nos. 87450/1998,255540/1997 and 245348/1996, or

[0421] acid hair dye compositions with a water-soluble polymer ofaromatic alcohols, lower alkylene carbonates, or the like as describedin Japanese Patent Application Laid-Open No. 53970/1998 and JapanesePatent Invention No. 23911/1973.

[0422] Preferred keratin fibers are human hair.

[0423] The dyes or dye precursors are suitable for all-over coloring ofthe hair, that is to say when coloring the hair on a first occasion, andalso for re-coloring subsequently, or coloration of locks or parts ofthe hair.

[0424] The dyes or dye precursors are applied to hair for examplethrough massage in by hand, a comb, a brush, or a bottle, or a bottle,which is combined with a comb or a nozzle.

[0425] In general, the dyes or dye precursors are applied to the hair ina formulation with further components, like adjuvants or additional dyesor dye precursors.

[0426] After the application of the dyeing composition the dyed hair iscustomary rinsed. Customary, the rinsing is conducted with water.

[0427] In a suitable embodiment of the processes of the presentinvention for dyeing human hair, the dyeing composition is not rinsedoff, but washed off with a commercially available hair shampoo.

[0428] In general, the dyed hair is dried after rinsing and/or washing.

[0429] Customary, drying is conducted with hot air by means of a drieror the like, since color migration to clothes and the like becomesscarcely caused.

[0430] A very suitable process for dyeing keratin fibers comprisescontacting the keratin fibers under alkaline conditions with at leastone capped diazotized compound and a coupler compound, with the provisothat the pH is adjusted in the range from 2 to 6 in the last processstep. Adjusting the pH is achieved in conventional manner by adding anacid as described for example in EP 962218, especially on page 3, lines12 to 16.

[0431] Acids are for example tartaric acid or citric acid, a citric acidgel, a suitable buffer solution with optionally an acid dye.

[0432] Preferred technical forms of acids are a solution, a gel, acream, foam, a conditioner, a emulsion, a shampoo and more preferred ashampoo or a conditioner.

[0433] In the context of the present invention, the expression “alkalinecondition”, denotes to all process steps without those wherein acidconditions are explicitly described.

[0434] In the processes for coloring according to the invention, whetheror not coloring is to be carried out in the presence of a further dyewill depend upon the color shade to be obtained.

[0435] In the context of the present invention, the expression “afurther dye”, denotes preferably an oxidation dye, a diazotisedcompound, a capped diazotised compound and/or coupler compound, or aciddye, especially selected a cationic, anionic or uncharged direct dye,especially a cationic dye selected from the group of the cationic dyesas described in WO 95/01772, especially on page 2, line 7 to page 4,line 1, and preferred on page 4, line 35 to page 8, line 21 with thegiven preferences, and as described in WO 01/66646, especially on page1, line 18 to page 3, line 16, or a mixture of at least two cationicdyes as described in WO 95/01772, especially on page 8, line 34 to page10, line 22.

[0436] The processes of the present invention for dyeing keratin fibers,in particular human hair, comprise after contacting the keratin fiberwith at least a compound of formula (1), and then leaving the fibers tostand, and

[0437] then rinsing the fibers.

[0438] The process for dyeing is for example described in WO 01/66646 onpage 15, line 32 to page 16, line 2.

[0439] Usually, the dyeing compositions are usually applied to the hairin an amount of from 50 to 100 g.

[0440] This composition is left on the fiber at 15 to 45° C. for 5 to 30minutes, and in particular for 10 to 20 minutes at 20 to 30° C.

[0441] Further preferred does a process for dyeing keratin fiberscomprise contacting the keratin fibers with at least one direct dye, abase and an oxidizing agent.

[0442] Compositions comprising at least one direct dye, especiallycompound of formula (1) and an oxidizing agent, are for exampledescribed in WO 97/20545, on page 3, line 24 to page 11, line 4, andespecially on page 4, line 9 to 17.

[0443] The composition comprising at least one direct dye, especially atleast a compound of formula (1), a base and an oxidizing agent isprepared by mixing at least one direct dye and a base, and then justbefore the dyeing of the hair, adding an oxidizing agent.

[0444] Alternatively, the oxidizing agent can be applied simultaneouslywith a composition comprising at least one dye, such as a compound offormula (1) and a base.

[0445] Preferably, the process for dyeing keratin fibers with at leaston direct dye comprises using a multi-compartment dyeing device or‘kits’ as described for example in WO 97/20545, especially on page 4,line 19 to line 27.

[0446] Suitable processes for enlightening dyeing, wherein a compound offormula (1) according to the invention can be used in combination withan oxidative agent are described in WO 97/20545, on page 11 to page 13.

[0447] Further preferred are processes for dyeing keratine fibers,especially compound of formula (1) with further cationic dyes, accordingto processes as described

[0448] in WO 95/01772, especially on page 10, line 24 to page 11, line16, and especially on page 11, line 29 to page 28, or

[0449] in WO 01/66646, especially on page 1, line 18 to page 3, line 16,and preferred from page 16, line 20 to page 22, or

[0450] in EP 970 685, especially on page 50, lines 15 to 43, andpreferred from page 50, line 46 to page 51, line 40, or

[0451] in DE-A-19 713 698, especially page 5, lines 26 to 60, or

[0452] a process of dyeing with direct dyes and oxidizing agent isdescribed in WO 97/20545, especially on page 10, line 10 to page 11,line 55 and preferably on page 11, line 6 to page 13, line 19.

[0453] Further preferred are processes for dyeing keratine fibers,especially compound of formula (1) with other dyes, which can becombined with a compound of formula (1) according to the presentinvention, are:

[0454] mixtures of at least two cationic dyes as described in WO95/01772, especially on page 11, lines 1 to 15, or

[0455] combinations of Pyrazolo-[1,5-a]-pyrimidines with at least onecationic dye as described in EP 998,908, especially on page 50, lines 15to 28, or

[0456] combinations of cationic dyes as described in FR-2788432,especially on page 49, line 28 to page 52, and preferred on page 50,lines 16 to 28, or

[0457] combinations of direct dyes and/or an oxidation dye and oxidizingagents in the form of permanent-wave fixing solution, especially withdirect dyes as described in DE-A-19 713 698, especially on page 2, lines12 to 23, especially on page 4, line 65 to page 5, line 59, orcombinations of cationic dyes and an oxidation dye of the developercompound type and oxidizing agents as described in EP 850 638,especially on page 29, line 42 to page 30, line 20 and preferred on page30, line 25 to page 32, line 30, or

[0458] combinations of an extemporaneous mixture of a composition (A)containing one or more oxidation dye precursors and optionally one ormore couplers, and of a composition (B), in powder form, containing oneor more direct dye, preferably cationic, optionally dispersed in anorganic pulverulent excipient and/or a mineral pulverulent excipient,and a composition (C) containing one or more oxidizing agent asdescribed in U.S. Pat. No. 6,190,421, especially in column 8, lines 43to 52, and preferably in column 8, line 55 to column 9, line 55, or aready-to-use composition comprising, at least one oxidation base, atleast one cationic direct dye and at least one enzyme of 2-electronoxidoreductase type in the presence of at least one donor for the saidenzyme as described in U.S. Pat. No. 6,228,129, especially in column 25,line 56 to column 27, line 9, or

[0459] a ready-to-use composition or multi-compartment dyeing devicecomprising compositions of at least one direct cationic dye and at leastone nitrated benzene dye as described in WO 99/20235 on page 34, line 27to page 37, or

[0460] a ready-to-use composition or multi-compartment dyeing devicecomprising compositions of at least one direct cationic dye and at leastone autooxidisable oxidation dye, especially benzene, indol and indolinederivatives as described in WO 99/20234, especially on page 32, line 20to page 35, oxidation dyeing compositions of at least one direct dye andat least one meta-Aminophenol derivative and at least one developercompound and an oxidizing agent as described in EP 850 636, especiallyon page 18, line 1 to page 22, line 11, or

[0461] oxidation dyeing compositions of at least one direct dye and atleast one developer compound selected from the group ofpara-Phenylenediamine derivatives and Bis-Phenylalkylenediamine and, andat least one coupler compound selected from the group of meta-Diphenolsand an oxidizing agent, as described in EP-A-850 637, especially on page19, line 24 to page 22, line 57,

[0462] cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives,as described in EP 998 908, especially on page 47, line 25 to page 50,line 29, or arianors and/or oxidative dyes, as described in FR-2 788432, especially on page 2, line 16 to page 3, line 16, and page 5, line19 to page 14, line 8, and combinations with cationic dyes as describedon page 14, line 23 and following, or

[0463] oxidative dye precursors (unsaturated aldehyde and couplercompounds), as described in German Patent Application 197 172 24,especially on page 3, line 36 to page 9 line 64.

[0464] The processes of coloring of keratin fibers, especially humanhair, with a compound of formula (1) according to the present inventionmay be combined with other direct dyes and oxidative dyes.

[0465] In a preferred embodiment of the present invention the processfor dyeing keratin fibers with direct dyes and oxidative dyes, inparticular human hair, comprises

[0466] a) contacting the keratin fibers with an oxidizing agent,optionally containing at least a compound of formula (1),

[0467] b) then contacting the keratin fibers with an oxidizing agentfree composition, optionally containing at least a compound of formula(1),

[0468] or

[0469] a) contacting the keratin fibers with an oxidizing agent freecomposition, optionally containing at least a compound of formula (1),

[0470] b) then contacting the keratin fibers with an oxidizing agent,optionally containing least a compound of formula (1), with the provisothat at least in one of the process steps a) or b) a compound of formula(1) is present.

[0471] The process of coloring with a compound of formula (1) accordingto the present invention may combined with a process for dyeing keratinfibers with direct dyes and oxidative dyes, which comprises

[0472] contacting the keratin fibers with least a compound of formula(1),

[0473] then contacting the keratin fibers with an oxidizing agent freecomposition.

[0474] Such process is for example described in DE 199 41 450,especially on page 5, lines 50 to 58, and on page 8, line 31 to 46.

[0475] Oxidizing agent is usually applied in form of an oxidizing agentcontaining composition.

[0476] Oxidizing agent free composition containing at least one couplercompound, at least one developer compound, a base and a reduction agent.

[0477] Customary, the oxidizing agent containing composition is evenlyapplied in a sufficient amount related to the amount of hair, usuallywith 30 to 200 g.

[0478] In general, the oxidizing agent containing composition is left onthe fiber at 15 to 45° C. for 0 to 15 minutes, and in particular for 0to 5 minutes.

[0479] Then the oxidizing agent free composition is applied to the hair.

[0480] In general, the direct dye and oxidizing agent free compositionis left on the fiber at 15 to 50° C. for 5 to 45 minutes, and inparticular for 10 to 25 minutes.

[0481] The coupler and developer compounds of the oxidizing agent freecomposition can be applied simultaneously or in succession. Preferred isa simultaneous application.

[0482] One preferred embodiment of the process is to wash the hair withshampoo and or a weak acid, such as citric acid or tartrate acid.

[0483] The direct dyes, which are stable to reduction can storedtogether with the oxidizing agent free compositions and are applicableas composition.

[0484] It is of advantage to prepare compositions of direct dyes, whichare not stable to reduction, with oxidizing agent free compositions justbefore the dyeing process.

[0485] Further, a direct dye and an oxidizing agent free composition canbe applied simultaneously or in succession.

[0486] A further process for the coloration of keratin fiber with directdyes and oxidation dyes, which can be used in combination with acompound of formula (1) according to the invention, comprises

[0487] mixing at least a compound of formula (1) and optionally at leastone coupler compound and at least one developer compound, and anoxidizing agent, which optionally contains at least one further directdye, and

[0488] then contacting the keratin fibers with the mixture as preparedin step a).

[0489] A further suitable process for the coloration of keratin fiberwith direct dyes and oxidation dyes, which can be used in combinationwith a compound of formula (1) according to the invention, comprises

[0490] mixing at least one autooxidable compound and at least onedeveloper compound and at least one compound of formula (1), and

[0491] then contacting the keratin fibers with the mixture prepared instep a).

[0492] The present invention relates also to a process, in which a dyeof formula (1), or cationic dye of formula (1) prepared according to aprocess according to the invention, or a composition according to theinvention,

[0493] and,

[0494] in succession in any desired order, or simultaneously,

[0495] a capped diazonium compound and

[0496] a water-soluble coupling component,

[0497] are applied to the material to be dyed under conditions in whichcoupling does not take place initially, and then the capped diazoniumcompound disposed on the material is caused to react with the couplingcomponent.

[0498] The first step of the dyeing method according to the inventioncomprises applying to the material to be dyed, in succession in anyorder or simultaneously, a capped diazonium compound and a water-solublecoupling component and, optionally, a cationic direct dye, theapplication being carried out under such conditions that coupling doesnot take place initially. This is effected, for example, by immersingthe material in a solution comprising the capped diazonium compound orthe coupling component and, optionally, a cationic direct dye, and then,if desired after rinsing and intermediate drying, immersing the materialin a solution of the second component. Preferably, however, the cappeddiazonium compound and the coupling component and, optionally, acationic direct dye, are present together in one solution. Suchsolutions can also be applied to the material by spraying or by similarmeasures, care having to be taken that penetration is adequate unless itis desired to dye only the upper layers. In that first step, thediazonium compound and the coupling component should not yet react witheach other, and that is preferably achieved by maintaining a pH value offrom 8 to 12, preferably from 9 to 11.

[0499] In the second step, the diazonium compound and the couplingcomponent are then caused to react, preferably by lowering the pH to avalue of from 5 to 2, especially from 3 to 4. The pH value is lowered incustomary manner by addition of an acid or a suitable buffer solution,especially citric acid or citric acid gel. If desired, a cationic directdye may be used in the second step. In any event, it is necessary for acationic direct dye to be used in one of steps 1 and 2 of the processaccording to the invention.

[0500] The dyed material is then finished in conventional manner, forexample by rinsing with water and subsequently drying.

[0501] Further, in the present invention especially preferred is aprocess for dyeing keratin fibers, in particular human hair, with cappeddiazotised compounds, which comprises,

[0502] contacting the keratin fibers, under alkaline conditions, with atleast one capped diazotised compound and a coupler compound, andoptionally an oxidizing agent, and optionally in the presence of afurther dye, and optionally with at least a compound of formula (1),

[0503] then adjusting the pH in the range of 6 to 2 by treatment withacid, optionally in the presence of a further dye, especially with, andoptionally at least a compound of formula (1), with the proviso that atleast in one step d) or e) at least a compound of formula (1) ispresent.

[0504] The capped diazotised compound and coupler compound andoptionally the oxidizing agent, can be applied in any desired ordersuccessively, or simultaneously.

[0505] Preferably, however, the capped diazotised compound and thecoupler compound are applied simultaneously, in a single composition.

[0506] Customary the dyeing composition is applied to the hair in anamount of from 50 to 100 g.

[0507] In the context of the present invention, the expression “alkalineconditions” denotes a pH in the range from 8 to 10, preferably 9-10,especially 9.5-10.

[0508] Adding bases, for example sodium carbonate, ammonia or sodiumhydroxide, to the hair or to the dye precursors, the capped diazotisedcompound and/or the water-soluble coupling component, or to coloringcompositions comprising the dye precursors, customarily achieve thealkaline conditions.

[0509] In the second stage, the diazotised compound and the couplercompound are then caused to react, preferably by lowering the pH byadding an acid to a value of from 6 to 2, especially from 3 to 4.

[0510] Acids are for example tartaric acid or citric acid, a citric acidgel, a suitable buffer solution with optionally an acid dye.

[0511] Preferred technical forms of acids are a solution, a gel, acream, foam, a conditioner, a emulsion, a shampoo and more preferred ashampoo or a conditioner.

[0512] The ratio of the amount of alkaline coloring composition appliedin the first stage to that of acid coloring composition applied in thesecond stage is preferably about from 1:3 to 3:1, especially about 1:1.

[0513] This first alkaline and then acid dyeing compositions each areleft on the fiber at 15 to 45° C. for 5 to 60 minutes, and in particularfor 5 to 45 minutes at 20 to 30° C.

[0514] A preferred embodiment of the process for dyeing keratin fiberswith capped diazotised compounds and a coupler compound, comprisescontacting the keratin fibers with more than one capped diazotisedcompound and/or more than one coupler compound.

[0515] Preferred is a process of the present invention for thecoloration of keratin fiber with capped diazotised compounds and atleast a compound of formula (1), comprises

[0516] mixing, under alkaline conditions, at least one with cappeddiazotised compound and at least one coupler compound and, optionallywith at least a compound of formula (I),

[0517] and optionally at least one developer compound; and an oxidizingagent, and, optionally with at least a compound of formula (1), and

[0518] then contacting the keratin fibers with the mixture as preparedin step a), and

[0519] then adjusting the pH in the range of 6 to 2 by treatment withacid, optionally in the presence of a further dye,

[0520] with the proviso that at least in one of the process a compoundof formula (1) is present.

[0521] More preferred is a process for dyeing keratin fibers with atleast one capped diazotized compound, which comprises

[0522] mixing under alkaline conditions, at least one capped diazotizedcompound and at least a compound of formula (1), a base and an oxidizingagent, and

[0523] then contacting the keratin fibers with the mixture as preparedin step a),

[0524] then adjusting the pH in the range of 6 to 2 by treatment withacid, optionally in the presence of a further dye.

[0525] Further, preferred is a process for the coloration of keratinfiber with capped diazotised compounds comprising

[0526] mixing under alkaline conditions, at least one with cappeddiazotised compound and at least one coupler compound and optionally atleast a compound of formula (1), and optionally at

[0527] least one developer compound, and optionally at least oneautooxidable compound, and then contacting the keratin fibers with themixture prepared in step a),

[0528] then adjusting the pH in the range of 6 to 2 by treatment withacid, and and optionally at least a compound of formula (1), andoptionally in the presence of a further dye, with the proviso that atleast in one of the process a compound of formula (1) is present.

[0529] A further preferred process for the two-step direct dyeing ofkeratin fibers, which can be used in combination with a compound offormula (1) according to the invention, is characterized in that,

[0530] contacting the keratin fibers with an oxidizing agent or anoxidizing agent containing composition,

[0531] then contacting the keratin fibers with at least one cappeddiazotised compound and at least a coupler compound and a compound offormula (1), and optionally an oxidizing agent free composition,

[0532] then adjusting the pH in the range of 6 to 2 by treatment withacid, optionally in the presence of a further dye.

[0533] or

[0534] contacting the keratin fibers with at least one capped diazotisedcompound and a coupler

[0535] compound and a compound of formula (1), and optionally anoxidizing agent free composition,

[0536] then contacting the keratin fibers with an oxidizing agent or anoxidizing agent containing composition,

[0537] then adjusting the pH in the range of 5 to 2 by treatment withacid, optionally in the presence of a further dye.

[0538] The present invention also concerns a process for the colorationof keratin fibers, especially human hair, with acid dyes, which can beused in combination with a compound of formula (1) according to theinvention.

[0539] The process comprises

[0540] contacting the keratin fiber with an acid dye and at least acompound of formula (1).

[0541] Customary, the dyeing composition comprising an acid dye isapplied to the hair in an amount of from 50 to 100 g.

[0542] This in a composition is left on the fiber at 15 to 45° C. for 1to 30 minutes, and in particular for 0 to 15 minutes at 20 to 30° C.

[0543] Preferably the hair is rinsed and than washed with shampoo andmore preferably not rinsed, but washed with shampoo.

[0544] The shampoo used herein includes a shampoo comprising 5-20% of ausual anionic surfactant such as an alkylsulfate or polyoxyethylenealkylsulfate.

[0545] Further, the present invention relates to a method of dyeingkeratin-containing fibers with the cationic reactive dyes, whichcomprises treating the fibers with the cationic reactive dyes defined atthe beginning or with the dye compositions according to the invention.

[0546] A preferred embodiment of the method according to the inventionfor dyeing keratin-containing fibers comprises treating the fibers witha dyeing solution, prepared according to the process of the invention,comprising a tinctorially effective amount of a cationic reactive dye offormula (1).

[0547] The cationic reactive dyes defined at the beginning are presentin the dye compositions according to the invention preferably in atinctorially effective amount of from 0.001% to 5%, especially from0.01% to 1%, based on the total dyestuff.

[0548] The keratin-containing fibers are usually treated with the dyeingsolution for about 30 minutes at 20-25° C.

[0549] A further preferred embodiment of the present invention relatesto a method of dyeing hair, which comprises treating the hair with

[0550] a) an acidic or alkaline permanent-wave solution, and

[0551] b) then with a dyeing solution, prepared according to the processof the invention, comprising a cationic reactive dye of formula (1).

[0552] Usually the keratin-containing fibers are treated with thepermanent-wave solution for about 3-10 minutes, preferably for 4-6minutes, at 20-25° C.

[0553] It is generally advisable to rinse the hair after treatment withthe dyeing solution and/or permanent-wave solution.

[0554] The present invention relates also to the use of the cationicreactive dyes defined at the beginning or of the dye compositionsaccording to the invention for dyeing keratin fibers, wool, leather,silk, cellulose or polyamides, especially for dyeing hair.

[0555] A preferred embodiment of the process according to the inventionfor dyeing keratin-containing fibers comprises treating the fibers witha dyeing solution, prepared according to the process of the invention,comprising a tinctorially effective amount of a cationic reactive dye.

[0556] The cationic reactive dyes are present in the dye compositionsaccording to the invention preferably in a tinctorially effective amountof from 0.001% to 5%, especially from 0.01% to 1%, based on the totaldyestuff.

[0557] The keratin-containing fibers are usually treated with the dyeingsolution for about 30 minutes at 20-25° C.

[0558] A further preferred embodiment of the present invention relatesto a method of dyeing hair, which comprises treating the hair with

[0559] a) an acidic or alkaline permanent-wave solution, and

[0560] b) then with a dyeing solution, prepared according to the processof the invention, comprising a cationic reactive dye.

[0561] Usually the keratin-containing fibers are treated with thepermanent-wave solution for about 3-10 minutes, preferably for 4-6minutes, at 20-25° C.

[0562] A preferred embodiment of the present invention relates to amethod of dyeing hair, which comprises treating the hair with a mixtureof

[0563] a) an acidic or alkaline permanent-wave solution comprising athiol derivative, and

[0564] b) a dyeing solution comprising a cationic dichlorotriazinereactive dye or a cationic monofluoromonochloropyrimidine reactive dye.

[0565] The dyes according to the invention are distinguished bybrilliant shades. They are suitable for dyeing organic material, such askeratin, wool, leather, silk, cellulose or polyamides, especiallykeratin-containing fibers, cotton or nylon, and preferably human hair.The dyeing obtained is distinguished by their depth of shade and theirgood fastness to washing properties, such as, for example, fastness tolight, shampooing and rubbing. The stability and storage stability ofthe dyes according to the invention are excellent. They are accordinglyespecially suitable for dyeing under oxidizing and reducing conditions.The advantage of the new dyes according to the present invention,especially those of formula (4), (5), or (6), is their stability againstreduction agents e. g. sodium sulfite and ascorbic acid. Therefore, theycan be combined with oxidation dyes in one emulsion.

[0566] The following Examples serve to illustrate the processes forcoloration without limiting the processes thereto. Unless specifiedotherwise, parts and percentages relate to weight. The amounts of dyespecified are relative to the material being colored.

EXAMPLES G (Application)

[0567] Compositions A, B, C, D, E, F and G for coloring human hairaccording to the following table below. D1- E6- G3- Compositions A B CD17** E17**** F* G9*** cetyl stearyl alcohol 11.0 11.0 11.00 11.00 11.0011.0 Oleth-5 5.0 5.0 5.0 5.0 5.0 5.0 oleic acid 2.5 2.5 2.5 2.5 2.5 2.5stearic acid 2.5 2.5 2.5 2.5 2.5 2.5 monoethanolamide coconut fatty acid2.5 2.5 2.5 2.5 2.5 2.5 monoethanolamide sodium lauryl sulfate 1.7 1.71.7 1.7 1.7 1.7 1,2-propanediol 1.0 1.0 1.0 1.0 1.0 1.0 ammoniumchloride 0.5 0.5 0.5 0.5 0.5 0.5 EDTA, tetrasodium 0.2 0.2 0.2 0.2 0.20.2 salt perfume 0.4 0.4 0.4 0.4 0.4 0.4 wheat protein 0.2 0.2 0.2 0.20.2 0.2 hydrolysate Silica 0.1 0.1 0.1 0.1 0.1 0.1 2,5-diaminotoluene0.7 0.7 sulfate 4-amino-2- 0.5 0.5 hydroxytoluene 2,5,6-triamino-4- 0.20.2 hydroxypyrimidine sulfate sodium sulfite 1.0 1.0 ascorbic acid 0.50.5 triazene of Example 9.33 15a coupler of Example 12.03 15 Directdye** 0.4 Direct dye*** 0.4 Direct dye**** 0.4 Black Color No. 401 0.1Purple Color 401 0.05 Orange Color No. 0.1 205 benzyl alcohol 2.0ethylene carbonate 10 propylene carbonate 15 Ethanol 10 Lactic acid 3.5sodium carbonate of solution pH 2.9 hydroxyethyl 1.5 cellulose Ammonia(25%) 9.2 9.2 9.2 9.2 9.2 9.2 composition: pH 9.8 9.8 9.8 9.8 9.8 9.8Water ad 100 add 100 ad 100 ad 100 ad 100 ad 100 ad 100 *F: dye mixtureknown from U.S. Pat. No. 6,248,314 **D1-D10 comprise the following dyes:in D1 the direct dye** is Basic Yellow 87; in D2 the direct dye** isBasic Orange 31; in D3 the direct dye** is or Basic Red 51; in D4 thedirect dye** is the cationic dye of example 4 as described in WO01/66646; in D5 the direct dye** is the cationic dye of example 6,compound of formula 106, as described WO 02/31056; in D6 the directdye** has the following formula (I) (I)

wherein R₁ is methyl, R₂ is benzyl, R₃ is hydrogen; in D7 the directdye** is a compound of formula (I) wherein R₁ is benzyl, R₂ is benzyl,R₃ is hydrogen; in D8 the direct dye** is a compound of formula (I)wherein R₁ is benzyl, R₂ is methyl, R₃ is hydrogen. In D10 the directdye** is a cationic dye of formula (3) as described in EP-A-714,954.**D11-D17 and ***D3-G9 comprise the following direct dyes: in D11 thedirect dye** and in G3 direct dye*** is a compound of formula (3),wherein X⁻ is cloride; in D12 the direct dye** and in G4 direct dye***is a compound of formula (4), wherein X⁻ is cloride; in D13 the directdye** and in G5 direct dye*** is a compound of formula (5), wherein X⁻is cloride; in D14 the direct dye** and in G6 direct dye*** is acompound of formula (6), wherein X⁻ is cloride; in D15 the direct dye**and in G7 direct dye*** is a compound of formula (7), wherein X⁻ iscloride; in D16 the direct dye** and in G8 direct dye*** is a compoundof formula (8), wherein X⁻ is fluoride; in D17 the direct dye** and inG9 direct dye*** is a compound of formula (9), wherein X⁻ is acetate;****E6-E17: In E6 the direct dye**** is identitcal the direct dye** ofD6; in E7 the direct dye**** is identical the direct dye** of D7; in E8the direct dye**** is identical the direct dye** of D8; E9 comprises asdirect dye Basic Yellow 87. in E10 the direct dye**** is identical thedirect dye** of D10; in E11 the direct dye**** is identical the directdye** of D11; in E12 the direct dye**** is identical the direct dye** ofD12; in E13 the direct dye**** is identical the direct dye** of D13; inE14 the direct dye**** is identical the direct dye** of D14; in E15 thedirect dye**** is identical the direct dye** of D15; in E16 the directdye**** is identical the direct dye** of D16; in E17 the direct dye****is identical the direct dye** of D17;

Example G/3

[0568] A strand of middle blond undamaged human hair is colored

[0569] 3a) with a mixture of 20 g of 6% hydrogen peroxide solution and acomposition consisting of 5 g each of compositions A, B, C and G5, andalternatively

[0570] 3b) first with 20 g of 6% hydrogen peroxide solution and thenwith 5 g of a composition A, and then with 5 g of composition B, andthen 5 g of composition C and 5 g of composition G5, or

[0571] 3c) first with 5 g of a composition A, 5 g of composition B, 5 gof composition C and 5 g of composition G5, and then with 20 g of 6%hydrogen peroxide solution.

[0572] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

[0573] A strong, intense, striking red coloration having good fastnessto washing and fastness to rubbing properties is obtained.

Example G/4

[0574] A strand of blond undamaged human hair is colored

[0575] 4a) with a composition consisting of 5 g each of compositions A,B and G9, and alternatively the coloring mixture is allowed to act onthe hair for 30 minutes at about 22° C. 10 g of a 2% strength aqueouscitric acid gel are then applied to the strand. After contact for 5minutes, the strand is rinsed thoroughly, shampooed and then dried.

[0576] A strong, intense, striking red coloration having good fastnessto washing and fastness to rubbing properties is obtained.

[0577] Example (4a/G9) is identical to Example 4a with the proviso thatG9 is replaced by G8.

[0578] Example (4a/G1) is identical to Example 4a with the proviso thatG9 is replaced by G7.

Example G/5

[0579] A strand of middle blond undamaged human hair is colored

[0580] 5a) with a mixture of 15 g of 6% hydrogen peroxide solution and acomposition consisting of 5 g each of compositions A, B and G6, andalternatively

[0581] 5b) first with 15 g of 6% hydrogen peroxide solution, and thenwith 5 g of a composition A, 5 g of composition, and B and 5 g ofcomposition G6.

[0582] 5c) first with 5 g of a composition A, 5 g of composition, and Band 5 g of composition G6, and then with 15 g of 6% hydrogen peroxidesolution.

[0583] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

[0584] A strong, intense, striking red coloration having good fastnessto washing and fastness to rubbing properties is obtained.

[0585] Example (5a/G5) is identical to Example 5a with the proviso thatG6 is replaced by G5.

[0586] Example (5a/G10) is identical to Example 5a with the proviso thatG6 is replaced by G9.

[0587] Example (5b/G9) is identical to Example 5b with the proviso thatG6 is replaced by G8.

[0588] Example (5b/G1) is identical to Example 5b with the proviso thatG6 is replaced by G3.

[0589] Example (5c/G5) is identical to Example 5c with the proviso thatG6 is replaced by G4.

[0590] Example (5c/G1) is identical to Example 5c with the proviso thatG6 is replaced by G7.

Example G/6

[0591] A strand of middle blond undamaged human hair is colored

[0592] 6a) with a mixture of 15 g of 6% hydrogen peroxide solution and acomposition consisting of 5 g each of compositions A, B and G6, andalternatively

[0593] 6b) first with 15 g of 6% hydrogen peroxide solution, and thenwith 5 g of a composition A, 5 g of composition B and 5 g of compositionG6, or

[0594] 6c) first with 5 g of a composition A, 5 g of composition B and 5g of composition G6, and then with 15 g of 6% hydrogen peroxidesolution.

[0595] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

[0596] A strong, intense, striking red coloration having good fastnessto washing and fastness to rubbing properties is obtained.

[0597] Example (6a/G5) is identical to Example 6a with the proviso thatG6 is replaced by G5.

[0598] Example (6a/G1) is identical to Example 6a with the proviso thatG6 is replaced by G3.

[0599] Example (6b/G9) is identical to Example 6b with the proviso thatG6 is replaced by G9.

[0600] Example (6b/G10) is identical to Example 6b with the proviso thatG6 is replaced by G8.

[0601] Example (6c/G5) is identical to Example 6c with the proviso thatG6 is replaced by G4.

[0602] Example (6c/G1) is identical to Example 6c with the proviso thatG6 is replaced by G7.

Example G/9

[0603] A strand of blond undamaged human hair is colored

[0604] 9a) with a mixture of 10 g of 6% hydrogen peroxide solution and acomposition consisting of 5 g each of compositions C and G6, andalternatively

[0605] 9b) with 10 g of 6% hydrogen peroxide solution and 5 g ofcomposition C and 5 g of composition G6.

[0606] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

[0607] A strong, intense, striking bluish red coloration having goodfastness to washing and fastness to rubbing properties is obtained.

[0608] Example (9a/G5) is identical to Example 9a with the proviso thatG6 is replaced by G5.

[0609] Example (9a/G1 ) is identical to Example 9a with the proviso thatG6 is replaced by G3.

[0610] Example (9b/G9) is identical to Example 9b with the proviso thatG6 is replaced by G9.

[0611] Example (9b/G10) is identical to Example 9b with the proviso thatG6 is replaced by G7.

Example G/10

[0612] A strand of blond undamaged human hair is colored

[0613] 10a) with a mixture of 10 g of 6% hydrogen peroxide solution anda composition consisting of 5 g each of compositions D1 and E11, andalternatively

[0614] 10b) first with 10 g of 6% hydrogen peroxide solution, and thenwith 5 g of composition D1 and 5 g of composition E11, or

[0615] 10c) first with 5 g of composition D1 and 5 g of composition E11,and then with 10 g of 6% hydrogen peroxide solution.

[0616] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

[0617] A strong, intense, striking bluish red coloration having goodfastness to washing and fastness to rubbing properties is obtained.

[0618] Example (10a/D2) is identical to Example 10a with the provisothat D1 is replaced by D2.

[0619] Example (10a/D3) is identical to Example 10a with the provisothat D1 is replaced by D3.

[0620] Example (10a/D4) is identical to Example 10a with the provisothat D1 is replaced by D4.

[0621] Example (10a/D5) is identical to Example 10a with the provisothat D1 is replaced by D5.

[0622] Example (10b/D2) is identical to Example 10b with the provisothat D1 is replaced by D2.

[0623] Example (10b/D3) is identical to Example 10b with the provisothat D1 is replaced by D3.

[0624] Example (10b/D4) is identical to Example 10b with the provisothat D1 is replaced by D4.

[0625] Example (10b/D5) is identical to Example 10b with the provisothat D1 is replaced by D5.

[0626] Example (10c/D2) is identical to Example 10c with the provisothat D1 is replaced by D2.

[0627] Example (10c/D3) is identical to Example 10c with the provisothat D1 is replaced by D3.

[0628] Example (10c/D4) is identical to Example 10c with the provisothat D1 is replaced by D4.

[0629] Example (10c/D5) is identical to Example 10c with the provisothat D1 is replaced by D5.

[0630] Example (10d/E12) is identical to Example 10a with the provisothat E11 is replaced by E12.

[0631] Example (10d/E19) is identical to Example 10a with the provisothat E11 is replaced by E19.

[0632] Example (10d/E16) is identical to Example 10a with the provisothat E11 is replaced by E16.

[0633] Example (10e/E15) is identical to Example 10b with the provisothat E11 is replaced by E15.

[0634] Example (10e/E12) is identical to Example 10b with the provisothat E11 is replaced by E12.

[0635] Example (10e/E16) is identical to Example 10b with the provisothat E11 is replaced by E16.

[0636] Example (10f/E12) is identical to Example 10c with the provisothat E11 is replaced by E12.

[0637] Example (10f/E19) is identical to Example 10c with the provisothat E11 is replaced by E19.

[0638] Example (10f/E16) is identical to Example 10c with the provisothat E11 is replaced by E16.

Example G/11

[0639] A strand of brown undamaged human hair is colored

[0640] 11a) with a mixture of 10 g of 6% hydrogen peroxide solution anda composition consisting of 5 g each of compositions C and E11, andalternatively

[0641] 11b) first with 10 g of 6% hydrogen peroxide solution, and thenwith 5 g of composition C and 5 g of composition E11, or

[0642] 11c) first with 5 g of composition C and 5 g of composition E11,and then with 10 g of 6% hydrogen peroxide solution.

[0643] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

[0644] A strong, intense, striking bluish red coloration having goodfastness to washing and fastness to rubbing properties is obtained.

[0645] Example (11a/E12) is identical to Example 11a with the provisothat E11 is replaced by E12.

[0646] Example (11a/E19) is identical to Example 11a with the provisothat E11 is replaced by E19.

[0647] Example (11a/E16) is identical to Example 11a with the provisothat E11 is replaced by E16.

[0648] Example (11b/E15) is identical to Example 11b with the provisothat E11 is replaced by E15.

[0649] Example (11b/E19) is identical to Example 11b with the provisothat E11 is replaced by E19.

[0650] Example (11b/E12) is identical to Example 11b with the provisothat E11 is replaced by E12.

[0651] Example (11c/E12) is identical to Example 11c with the provisothat E11 is replaced by E12.

[0652] Example (11c/E19) is identical to Example 11c with the provisothat E11 is replaced by E19.

[0653] Example (11c/E15) is identical to Example 11c with the provisothat E11 is replaced by E15.

Example G/12

[0654] A strand of blond undamaged human hair is colored

[0655] 12a) with a mixture of 5 g of 6% hydrogen peroxide solution and 5g of composition G6, and alternatively

[0656] 12b) first with 5 g of 6% hydrogen peroxide solution, and thenwith 5 g of a composition G6, or

[0657] 12c) first with 5 g of a composition G6, and then with 5 g of 6%hydrogen peroxide solution.

[0658] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C.

[0659] After contact for 30 minutes, without being washed out, 10 g of adye mixture F is applied to the hair. The hair is then combed throughthoroughly, whereupon its pH becomes about 3. Then, after a contactperiod of 15 minutes, the hair is rinsed thoroughly with water anddried.

[0660] Example (12a/G5) is identical to Example 12a with the provisothat G6 is replaced by G5.

[0661] Example (12a/G1) is identical to Example 12a with the provisothat G6 is replaced by G7.

Example G/13

[0662] A strand of blond undamaged human hair is colored with 10 g ofcomposition G6,

[0663] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C.

[0664] After contact for 30 minutes, without being washed out, 10 g of adye mixture F is applied to the hair. The hair is then combed throughthoroughly, whereupon its pH becomes about 3. Then, after a contactperiod of 15 minutes, the hair is rinsed thoroughly with water anddried.

[0665] Example (13/G5) is identical to Example G/13 with the provisothat G6 is replaced by G5.

[0666] Example (13/G9) is identical to Example G/13 with the provisothat G6 is replaced by G9.

Example G/15

[0667] A strand of blond undamaged human hair is colored with 10 g of acomposition G6.

[0668] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. After contact the strand is rinsed thoroughly, shampooedand then dried.

[0669] A strong, intense, striking red coloration having good fastnessto washing and fastness to rubbing properties is obtained.

[0670] Example (15/G5) is identical to Example 15 with the proviso thatG6 is replaced by G5.

[0671] Example (15/G9) is identical to Example 15 with the proviso thatG6 is replaced by G9.

Example G/16

[0672] A strand of blond undamaged human hair is colored

[0673] 16a) with a mixture of 5 g of 6% hydrogen peroxide solution and 5g of composition G6, and alternatively

[0674] 16b) first with 5 g of 6% hydrogen peroxide solution, and thenwith 5 g of a composition G6, or

[0675] 16c) first with 5 g of a composition G6, and then with 5 g of 6%hydrogen peroxide solution.

[0676] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 15 minutes, the strand isrinsed thoroughly, shampooed and then dried.

[0677] A strong, intense, striking red coloration having good fastnessto washing and fastness to rubbing properties is obtained.

[0678] Example (16a/G5) is identical to Example 16a with the provisothat G6 is replaced by G5.

[0679] Example (16a/G9) is identical to Example 16a with the provisothat G6 is replaced by G9.

[0680] Example (16b/G10) is identical to Example 16b with the provisothat G6 is replaced by G4.

[0681] Example (16b/G1) is identical to Example 16b with the provisothat G6 is replaced by G3.

[0682] Example (16c/G1) is identical to Example 16c with the provisothat G6 is replaced by G7.

[0683] Example (16c/G5) is identical to Example 16c with the provisothat G6 is replaced by G8.

Example G/22

[0684] A strand of blond undamaged human hair is colored with 10 g of acomposition G6. Then the pH is adjusted in the range of pH 5 to 8 byadding citric acid.

[0685] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. After contact the strand is rinsed thoroughly, shampooedand then dried.

[0686] A strong, intense, striking red coloration having good fastnessto washing and fastness to rubbing properties is obtained.

[0687] Example (22/G5) is identical to Example G/22 with the provisothat G6 is replaced by G5.

[0688] Example (22/G1) is identical to Example G/22 with the provisothat G6 is replaced by G3.

Example G/23

[0689] A strand of brown undamaged human hair is colored

[0690] 11a) with a mixture of 15 g of 6% hydrogen peroxide solution anda composition consisting of 5 g each of compositions C, D1 and E11, andalternatively

[0691] 11b) first with 10 g of 6% hydrogen peroxide solution, and thenwith 5 g each of compositions C, D1 and E11 or

[0692] 11c) first with 5 g each of compositions C, D1 and E11, then with10 g of 6% hydrogen peroxide solution.

[0693] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

[0694] A strong, intense, striking bluish red coloration having goodfastness to washing and fastness to rubbing properties is obtained.

[0695] Example (23a/D2) is identical to Example 23a with the provisothat D1 is replaced by D2.

[0696] Example (23a/D3) is identical to Example 23a with the provisothat D1 is replaced by D3.

[0697] Example (23a/D4) is identical to Example 23a with the provisothat D1 is replaced by D4.

[0698] Example (23a/D5) is identical to Example 23a with the provisothat D1 is replaced by D5.

[0699] Example (23b/D2) is identical to Example 23b with the provisothat D1 is replaced by D2.

[0700] Example (23b/D3) is identical to Example 23b with the provisothat D1 is replaced by D3.

[0701] Example (23b/D4) is identical to Example 23b with the provisothat D1 is replaced by D4.

[0702] Example (23b/D5) is identical to Example 23b with the provisothat D1 is replaced by D5.

[0703] Example (23c/D2) is identical to Example 23c with the provisothat D1 is replaced by D2.

[0704] Example (23c/D3) is identical to Example 23c with the provisothat D1 is replaced by D3.

[0705] Example (23c/D4) is identical to Example 23c with the provisothat D1 is replaced by D4.

[0706] Example (23c/D5) is identical to Example 23c with the provisothat D1 is replaced by D5.

[0707] Example (23a/E12) is identical to Example 23a with the provisothat E11 is replaced by E12.

[0708] Example (23a/E16) is identical to Example 23a with the provisothat E11 is replaced by E16.

[0709] Example (23a/E15) is identical to Example 23a with the provisothat E11 is replaced by E15.

[0710] Example (23b/E12) is identical to Example 23b with the provisothat E11 is replaced by E12.

[0711] Example (23b/E19) is identical to Example 23b with the provisothat E11 is replaced by E19.

[0712] Example (23b/E15) is identical to Example 23b with the provisothat E11 is replaced by E15.

[0713] Example (23c/E16) is identical to Example 23c with the provisothat E11 is replaced by E16.

[0714] Example (23c/E12) is identical to Example 23c with the provisothat E11 is replaced by E12.

[0715] Example (23c/E19) is identical to Example 23c with the provisothat E11 is replaced by E19.

[0716] Example (23a/D2/E712) is identical to Example 23a/D2 with theproviso that that E11 is replaced by E12.

[0717] Example (23a/D3/E15) is identical to Example 23a/D3 with theproviso that that E11 is replaced by E15.

[0718] Example (23a/D4/E9) is identical to Example 23a/D4 with theproviso that E11 is replaced by E7.

[0719] Example (23b/D2/E1 9) is identical to Example 23b/D2 with theproviso that that E11 is replaced by E19.

[0720] Example (23b/D3/E12) is identical to Example 23b/D3 with theproviso that that E11 is replaced by E12.

[0721] Example (23b/D4/E16) is identical to Example 23b/D4 with theproviso that E11 is replaced by E16.

[0722] Example (23c/D2/E12) is identical to Example 23c/D2 with theproviso that that E11 is replaced by E12.

[0723] Example (23c/D3/E15) is identical to Example 23c/D3 with theproviso that that E11 is replaced by E15.

[0724] Example (23c/D4/E19) is identical to Example 23c/D4 with theproviso that E11 is replaced by E19.

Example G/24

[0725] A strand of blond undamaged human hair is colored

[0726] 24a) with a mixture of 5 g of 6% hydrogen peroxide solution and acomposition consisting of 5 g of composition E11 and alternatively

[0727] 24b) first with 5 g of 6% hydrogen peroxide solution, and thenwith 5 g of composition 11 or

[0728] 25c) first with 5 g of composition E11 and then with 5 g of 6%hydrogen peroxide solution.

[0729] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

[0730] A strong, intense, striking bluish red coloration having goodfastness to washing and fastness to rubbing properties is obtained.

[0731] Example (24a/E12) is identical to Example 24a with the provisothat E11 is replaced by E12.

[0732] Example (24b/E19) is identical to Example 24a with the provisothat E11 is replaced by E19.

[0733] Example (24c/E15) is identical to Example 24a with the provisothat E11 is replaced by E15.

[0734] Example (24b/E16) is identical to Example 24b with the provisothat E11 is replaced by E16.

[0735] Example (24b/E15) is identical to Example 24b with the provisothat E11 is replaced by E15.

[0736] Example (24b/E12) is identical to Example 24b with the provisothat E11 is replaced by E12.

[0737] Example (25c/E16) is identical to Example 25c with the provisothat E11 is replaced by E16.

[0738] Example (25c/E19) is identical to Example 25c with the provisothat E11 is replaced by E19.

[0739] Example (25c/E12) is identical to Example 25c with the provisothat E11 is replaced by E12.

Example G/25

[0740] A strand of blond undamaged human hair is colored with

[0741] 25a) 5 g of a composition according to the following tablebehentrimonium chloride 3.8 g cetylalcohol   4 g phenoxyethanol andisobutylparaben 0.5 g perfume 0.1 g Direct Dye, of formula (6), whereinX⁻ is 0.5 g chloride Monoethanolamine ad pH 6.5 Water ad100

[0742] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. After contact the strand is rinsed and then dried.

[0743] A strong, intense, striking coloration having good fastness towashing and fastness to rubbing properties is obtained.

[0744] Example (25a/G5) is identical to Example 25a with the provisothat of formula (6), wherein X⁻ is chloride is replaced by of formula(5), wherein X⁻ is chloride.

[0745] Example (25a/G9) is identical to Example 25a with the provisothat of formula (6), wherein X⁻ is chloride is replaced by of formula(7), wherein X⁻ is acetate.

[0746] Example (25a/G1) is identical to Example 25a with the provisothat of formula (6), wherein X⁻ is chloride is replaced by of formula(3), wherein X⁻ is chloride.

Example G/26

[0747] 26a)

[0748] 2 g of a composition A according to the following tableCOMPOSITION A sodium stearat 11.0 g aluminium distearat  2.7 g sodiumlaurylsulfat(Duponol C)  1.0 g disperse silicic acid (Aerosil 200)  9.1g hydroxypropylcellulose  2.7 g ammoniumpersulfat 19.0 g sodiummetasilicat 12.0 g disodium salt of ethylentetraminacetic acid  1.0 gpotassium persulfat 31.5 g

[0749] and 3.6 g of a composition B according to the following tableCOMPOSITION B water 188 g hydrogenperoxide  12 g

[0750] are mixed to a homogenous mixture. This homogenous mixture isallowed to act on a strand of blond undamaged human hair for 30 minutesat about 22° C. After contact the strand is rinsed, shampooed.

[0751] Then the hair is colored with 5 g of a composition according tothe following table behentrimonium chloride 3.8 g cetylalcohol   4 gphenoxyethanol and isobutylparaben 0.5 g perfume 0.1 g Direct Dye, offormula (6), wherein X⁻ is 0.5 g chloride monoethanolamine ad pH 6.5water ad100

[0752] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. After contact the strand is rinsed and then dried.

[0753] A strong, intense, striking coloration having good fastness towashing and fastness to rubbing properties is obtained.

[0754] Example (26a/G5) is identical to Example 26a with the provisothat direct dye of formula (6), wherein X⁻ is chloride is replaced bydirect dye of formula (5), wherein X⁻ is chloride.

[0755] Example (26a/G9) is identical to Example 26a with the provisothat direct dye of formula (6), wherein X⁻ is chloride is replaced bydirect dye of formula (3), wherein X⁻ is chloride.

[0756] Example (26a/G10) is identical to Example 26a with the provisothat direct dye of formula (6), wherein X⁻ is chloride is replaced bydirect dye of formula (4), wherein X⁻ is chloride.

Example G/27

[0757] 27a)

[0758] 2 g of a composition A according to the following tableCOMPOSITION A sodium stearat 11.0 g aluminium distearat  2.7 g sodiumlaurylsulfat(Duponol C)  1.0 g disperse silicic acid (Aerosil 200)  9.1g hydroxypropylcellulose  2.7 g ammoniumpersulfat 19.0 g sodiummetasilicat 12.0 g disodium salt of ethylentetraminacetic acid  1.0 gpotassium persulfat 31.5 g Direct Dye, of formula (3), wherein X⁻ is  10 g chloride

[0759] and 4 g of a composition B according to the following tableCOMPOSITION B water 188 g hydrogenperoxide  12 g

[0760] are mixed to a homogenous mixture. This homogenous mixture isallowed to act on a strand of blond undamaged human hair for 30 minutesat about 22° C. After contact the strand is rinsed, shampooed and dried.

[0761] Example (27a/G5) is identical to Example 27a with the provisothat direct dye of formula (3), wherein X⁻ is chloride is replaced bydirect dye of formula (6), wherein X⁻ is chloride.

[0762] Example (27a/G1) is identical to Example 27a with the provisothat direct dye of formula (3), wherein X⁻ is chloride is replaced bydirect dye of formula (5), wherein X⁻ is chloride.

[0763] Example (27a/G9) is identical to Example 27a with the provisothat direct dye of formula (3), wherein X⁻ is chloride is replaced bydirect dye of formula (7), wherein X⁻ is chloride.

Example G/28

[0764] 28a)

[0765] 2 g of a composition A according to the following tableCOMPOSITION A sodium stearat 11.0 g aluminium distearat  2.7 g sodiumlaurylsulfat(Duponol C)  1.0 g disperse silicic acid (Aerosil 200)  9.1g hydroxypropylcellulose  2.7 g ammoniumpersulfat 19.0 g sodiummetasilicat 12.0 g disodium salt of ethylentetraminacetic acid  1.0 gpotassium persulfat 31.5 g Dye, **D1-D5   10 g

[0766] and 4 g of a composition B according to the following tableCOMPOSITION B water 188 g hydrogenperoxide  12 g

[0767] are mixed to a homogenous mixture. This homogenous mixture isallowed to act on a strand of blond undamaged human hair for 30 minutesat about 22° C. After contact the strand is rinsed, shampooed.

[0768] Then the hair is colored with 5 g of a composition according tothe following table behentrimonium chloride 3.8 g cetylalcohol   4 gphenoxyethanol and isobutylparaben 0.5 g perfume 0.1 g Direct Dye, offormula (4), wherein X⁻ is 0.5 g chloride monoethanolamine ad pH 6.5water ad100

[0769] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. After contact the strand is rinsed and then dried.

[0770] A strong, intense, striking coloration having good fastness towashing and fastness to rubbing properties is obtained.

[0771] Example (28a/G5) is identical to Example 28a with the provisothat direct dye of formula (4), wherein X⁻ is chloride is replaced bydirect dye of formula (7), wherein X⁻ is chloride.

[0772] Example (28a/G10) is identical to Example 28a with the provisothat direct dye of formula (4), wherein X⁻ is chloride is replaced bydirect dye of formula (3), wherein X⁻ is chloride.

[0773] Example (28a/G9) is identical to Example 28a with the provisothat direct dye of formula (4), wherein X⁻ is chloride is replaced bydirect dye of formula (5), wherein X⁻ is chloride.

Example G/30

[0774] 30a)

[0775] 2 g of a composition A according to the following tableCOMPOSITION A sodium stearat 11.0 g aluminium distearat  2.7 g sodiumlaurylsulfat(Duponol C)  1.0 g disperse silicic acid (Aerosil 200)  9.1g hydroxypropylcellulose  2.7 g ammoniumpersulfat 19.0 g sodiummetasilicat 12.0 g disodium salt of ethylentetraminacetic acid  1.0 gpotassium persulfat 31.5 g

[0776] is mixed with 2 g of a composition C,

[0777] and 4 g of a composition B according to the following tableCOMPOSITION B water 188 g hydrogenperoxide  12 g

[0778] to a homogenous mixture. This homogenous mixture is allowed toact on a strand of blond undamaged human hair for 30 minutes at about22° C. After contact the strand is rinsed and shampooed.

[0779] Then the hair is colored with 5 g of a composition according tothe following table behentrimonium chloride 3.8 g cetylalcohol   4 gphenoxyethanol and isobutylparaben 0.5 g perfume 0.1 g Direct Dye, offormula (4), wherein X⁻ is 0.5 g chloride monoethanolamine ad pH 6.5water ad100

[0780] The coloring mixture is allowed to act on the hair for 30 minutesat about 22° C. After contact the strand is rinsed and then dried.

[0781] A strong, intense, striking coloration having good fastness towashing and fastness to rubbing properties is obtained.

[0782] Example (30a/G5) is identical to Example 30a with the provisothat direct dye of formula (4), wherein X⁻ is chloride is replaced bydirect dye of formula (7), wherein X⁻ is acetate.

[0783] Example (30a/G10) is identical to Example 30a with the provisothat direct dye of formula (4), wherein X⁻ is chloride is replaced bydirect dye of formula (7), wherein X⁻ is fluoride.

[0784] Example (30a/G9) is identical to Example 30a with the provisothat direct dye of formula (4), wherein X⁻ is chloride is replaced bydirect dye of formula (7), wherein X⁻ is chloride.

Example G/31

[0785] 31a)

[0786] 2 g of a composition A according to the following tableCOMPOSITION A sodium stearat 11.0 g aluminium distearat  2.7 g sodiumlaurylsulfat(Duponol C)  1.0 g disperse silicic acid (Aerosil 200)  9.1g hydroxypropylcellulose  2.7 g ammoniumpersulfat 19.0 g sodiummetasilicat 12.0 g disodium salt of ethylentetraminacetic acid  1.0 gpotassium persulfat 31.5 g

[0787] is mixed with a 2.0 g of a composition E11

[0788] and 6 g of a composition B according to the following tableCOMPOSITION B water 188 g hydrogenperoxide  12 g

[0789] to a homogenous mixture. This homogenous mixture is allowed toact on a strand of blond undamaged human hair for 30 minutes at about22° C. After contact the strand is rinsed, shampooed and dried.

[0790] Example (31a/E12) is identical to Example 31a with the provisothat E11 is replaced by E12.

[0791] Example (31b/E15) is identical to Example 31a with the provisothat E11 is replaced by E15.

[0792] Example (31c/E19) is identical to Example 31a with the provisothat E11 is replaced by E19.

Example G/32

[0793] 32a)

[0794] 2 g of a composition A according to the following tableCOMPOSITION A sodium stearat 11.0 g aluminium distearat  2.7 g sodiumlaurylsulfat(Duponol C)  1.0 g disperse silicic acid (Aerosil 200)  9.1g hydroxypropylcellulose  2.7 g ammoniumpersulfat 19.0 g sodiummetasilicat 12.0 g disodium salt of ethylentetraminacetic acid  1.0 gpotassium persulfat 31.5 g

[0795] is mixed with a 2.0 g of a composition C as given in example G asgiven above, and 2.0 g of a direct dye, direct Dye, of formula (4),wherein X⁻ is chloride,

[0796] and 8 g of a composition B according to the following tableCOMPOSITION B water 188 g hydrogenperoxide  12 g

[0797] to a homogenous mixture. This homogenous mixture is allowed toact on a strand of blond undamaged human hair for 30 minutes at about22° C. After contact the strand is rinsed, shampooed and dried.

[0798] Example (32a/G5) is identical to Example 32a with the provisothat direct dye of formula (4), wherein X⁻ is chloride is replaced bydirect dye of formula (7), wherein X⁻ is chloride.

[0799] Example (32a/G1) is identical to Example 32a with the provisothat direct dye of formula (4), wherein X⁻ is chloride is replaced bydirect dye of formula (3), wherein X⁻ is chloride.

[0800] Example (32a/G9) is identical to Example 32a with the provisothat direct dye of formula (4), wherein X⁻ is chloride is replaced bydirect dye of formula (5), wherein X⁻ is chloride.

Example G/33

[0801] 33a

[0802] Composition (A′) polyglycerol alcohol with 2 mols of glycerol 4.0 g polyglycerol alcohol with 4 mols of glycerol  5.69 g of 78%(M.A.) oil acid  3.0 g oil amine with 2 mols ethylenoxide available  7.0g from ETHOMEEN O12 from AKZO Laurylamine succinamate of  3.0 gdiethylaminopropylene, salt of sodium with 55%. oil alcohol  5.0 gdiethynolamide of oil acid  12.0 g propylenglycol  3.5 g ethylenalcohol 7.0 g monobutylether of diethylenglycol  0.5 g monomethylether ofpropylenglycol  0.5 g sodium metabisulfite as solution a 35% 0.455 gammonium acetate  0.8 g paraphenylendiamine  0.35 g 1,3-dihydroxybenzene 0.4 g 3-amino phenol  0.03 g 2,4-diamino-1-(β-hydroxyethyloxy)benzene,0.012 g 2HCl 1,3-bis-[(4-aminophenyl)2-hydroxyethyl)- 0.037 gamino]-2-propanol, 4HCl 1,3-dihydroxy-2-methyl-benzene  0.2 gantioxidant qs parfume qs ammonia 20% de NH₃  10.0 g water   100 g

[0803] Composition (B′) direct dye of formula (3), wherein X⁻ is  20 gchloride, in powder form oil of parafine  3 g cationic polymeric powder(Merquat 280 Dry  10 g de Calgon) sawdust 100 g

[0804] Composition (C′) hydrogenperoxide 20% by volume

[0805] Just before the coloration of human hair a mixture of 1equivalent of weight of Composition (A′), 01 equivalent of weight ofcomposition (B′) and 1 equivalent of weight of composition (C′) ismixed.

[0806] The pH of the mixture is adjusted to 9.8.

[0807] The coloring mixture is applied on human grey hair. This mixtureis allowed to act on a strand of blond undamaged human hair for 30minutes. After contact the strand is rinsed, shampooed and dried.

[0808] Example (33a/G5) is identical to Example 33a with the provisothat direct dye of formula (3), wherein X⁻ is chloride is replaced bydirect dye of formula (5), wherein X⁻ is chloride.

[0809] Example (33a/G1) is identical to Example 33a with the provisothat direct dye of formula (3), wherein X⁻ is chloride is replaced bydirect dye of formula (4), wherein X⁻ is chloride.

[0810] Example (33a/G9) is identical to Example 33a with the provisothat direct dye of formula (3), wherein X⁻ is chloride is replaced bydirect dye of formula (7), wherein X⁻ is chloride.

Example G/34

[0811] 34a)

[0812] Composition (B′) direct dye of formula (4), wherein X⁻ is  20 gchloride, in powder form oil of parafine  3 g cationic polymeric powder(Merquat 280 Dry  10 g de Calgon) sawdust 100 g

[0813] Composition (C′): hydrogenperoxide 20% by volume 100 g

[0814] Just before the coloration of human hair a mixture of 1equivalent of weight of Composition (B′), and 1 equivalent of weight ofcomposition (C′) is mixed.

[0815] The pH of the mixture is adjusted to 9.8.

[0816] The coloring mixture is applied on human grey hair. This mixtureis allowed to act on a strand of blond undamaged human hair for 30minutes. After contact the strand is rinsed, shampooed and dried.

[0817] Example (34a/G5) is identical to Example 34a with the provisothat direct dye of formula (4), wherein X⁻ is chloride is replaced bydirect dye of formula (5), wherein X⁻ is chloride.

[0818] Example (34a/G9) is identical to Example 34a with the provisothat direct dye of formula (4), wherein X⁻ is chloride is replaced bydirect dye of formula (7), wherein X⁻ is chloride.

[0819] Example (34a/G10) is identical to Example 34a with the provisothat direct dye of formula (4), wherein X⁻ is chloride is replaced bydirect dye of formula (6), wherein X⁻ is chloride.

Example G/35

[0820] 35a)

[0821] Composition (B′) direct dye, direct dye of formula (5), wherein 20 g X⁻ is chloride, in powder form oil of parafine  3 g cationicpolymeric powder (Merquat 280 Dry  10 g de Calgon) sawdust 100 g

[0822] Composition (C′): hydrogenperoxide 20% by volume 100 g

[0823] Just before the coloration of human hair a mixture of 1equivalent of weight of Composition (B′), and 1 equivalent of weight ofcomposition (C′) is mixed.

[0824] The pH of the mixture is adjusted to 9.8 with ammonia 20% byvolume.

[0825] The coloring mixture is applied on human grey hair. This mixtureis allowed to act on a strand of blond undamaged human hair for 30minutes. After contact the strand is rinsed, shampooed and dried.

[0826] Example (35a/G1) is identical to Example 35a with the provisothat direct dye of formula (5), wherein X⁻ is chloride is replaced bydirect dye of formula (6), wherein X⁻ is chloride.

[0827] Example (35a/G9) is identical to Example 35a with the provisothat direct dye of formula (5), wherein X⁻ is chloride is replaced bydirect dye of formula (3), wherein X⁻ is chloride.

[0828] Example (35a/G5) is identical to Example 35a with the provisothat direct dye of formula (5), wherein X⁻ is chloride is replaced bydirect dye of formula (7), wherein X⁻ is acetate.

Example 36

[0829] A strongly alkaline 10% solution of a non-ionic surfactant(Plantaren 2000, Henkel) is adjusted to pH 9.5 using citric acid. 0.1%of the dye of formula (11), example 46, according to the presentapplication, is dissolved therein and a strand of human hair, bleachedwhite, is treated with that dye solution at 293 K. After only a shortperiod of time, the strand has been dyed an orange shade, which is stillvery intensive even shampooing ten times. The dye also has a strongaffinity to undamaged hair. In that case, too, the wash fastness is verygood. The light fastness on damaged and undamaged hair is excellent. Theperm fastness is on un- and damaged hair very good as well.

Example 37

[0830] A 10% solution of a non-ionic surfactant (Plantaren 2000, Henkel)is adjusted to pH 5.5 using citric acid. 0.1% of the dye of formula(12), example 47, as given above, is dissolved therein and a strand ofmiddle blonde undamaged human hair is treated with the dye solution atroom temperature. After only a short period of time, the strand has beendyed a red shade, which has a good wash, perm and light fastness.

Example 38

[0831] A dye emulsion, containing

[0832] 0.1% of the dye of formula (14) according to example 49 of thepresent application,

[0833] 3.5% cetearyl alcohol,

[0834] 1.0% ceteareth 80,

[0835] 0.5% glyceryl mono-di-stearate,

[0836] 3.0% stearamide DEA,

[0837] 1.0% stearamphopropyl sulfonate,

[0838] 0.5% polyquarternium-6 and

[0839] water ad 100%,

[0840] is applied for 30 minutes, at room temperature, to bleached humanhair, and rinsed. The result is a very attractive vibrant red dyeingwith good fastnesses.

Example 39

[0841] A dye emulsion with pH=9.8, containing: dye of formula (11) ofexample 1.0 46 according to the present application cetylstearylalcohol11.0 oleth-5 5.0 oleic acid 2.5 stearic acid 2.5 monoethanolamide cocofatty acid 2.5 monoethanolamide sodium laurylsuphate 1.7 1,2-propanediol1.0 ammoniumchloride 0.5 EDTA, tetrasodiumsalt 0.2 perfume 0.4comproteinhydrolysate 0.2 silica 0.1

[0842] is mixed with the same weight of 6% hydrogen peroxide solutionand the mixture is immediately applied to a tress of brown hair. After30 minutes the tress is rinsed, shampooed, rinsed and dried.

[0843] The color result is a very brilliant red shade.

Example 40

[0844] A dye emulsion with pH 9.8, containing: dye of formula (11) ofexample 0.5 46 according to the present application cetylstearylalcohol11.0 oleth-5 5.0 oleic acid 2.5 stearic acid 2.5 monoethanolamide cocofatty acid 2.5 monoethanolamide sodium laurylsuphate 1.7 sodiumsulphite1.0 ascorbic acid 0.5 1,2-propanediol 1.0 ammoniumchloride 0.5 EDTA,tetrasodiumsalt 0.2 perfume 0.4 comproteinhydrolysate 0.2 silica 0.1toluene-2,5-diamine sulfate 0.07 resorcinol 0.02 2-amino-6-chloro-4-0.01 nitrophenol 4-amino-m-cresol 0.03 2-amino-3-hydroxypyridine 0.00 1

is mixed with the same weight of 6% hydrogen peroxide solution and themixture is immediately applied to a tress of brown hair. After 30minutes the tress is rinsed, shampooed, rinsed and dried.

[0845] The color result is a very brilliant ruby shade.

Example 41

[0846] A strongly alkaline 10% solution of a non-ionic surfactant(Plantaren 2000, Henkel) is adjusted to pH 9.5 using citric acid. 0.2%of dye of formula (11) of example 46 according to the presentapplication and 0.1% of the dye formula (17) of example 52 according tothe present application are dissolved therein and a strand of middleblonde undamaged human hair is treated with the dye solution at roomtemperature. After only 10 minutes, the strand has been dyed anintensive orange shade, which has a good wash, perm and light fastness.

Example 42

[0847] A strongly alkaline 10% solution of a non-ionic surfactant(Plantaren 2000, Henkel) is adjusted to pH 9.5 using citric acid. 0.2%of dye of formula (11) of example 46 according to the presentapplication and 0.1% of the dye formula

[0848] are dissolved therein and a strand of dark blonde undamaged humanhair is treated with the dye solution at room temperature. After 20minutes, the strand has been dyed an intensive red-copper shade, whichhas a good wash, perm and light fastness.

Example 43

[0849] A strand of bleached human hair is treated with 10 g of a dyecomposition having a pH of 9.8, comprising 5 g of a 6% hydrogen peroxidesolution and 5 g of a composition A given below

[0850] Composition A oleic acid 10.0 toluene-2,5-diamine sulfate 0.07resorcinol 0.02 2-amino-6-chloro-4- 0.01 nitrophenol 4-amino-m-cresol0.03 2-amino-3-hydroxypyridine 0.001 sodium sulfite 1.0 ascorbinic acid0.5 water Ad 100

[0851] After 15 minutes, 10 g of a 12.5% citric acid gel, comprising thedye of formula (11) of example 46 according to the present applicationis applied on the hair and combed, so that the hair has a pH of 7. After15 minutes the hair is washed with water, rinsed and dried. The strandhas been dyed in an intensive red shade, which has a good wash and lightfastness.

Example 44

[0852] A strand of middle blonde human hair is dyed with 10 g of acomposition having a pH of 9.8, which is obtained by mixing 5g of 6%hydrogen peroxide solution and 5 g of a composition A as given above inexample 50. After 15 minutes, the pH of the hair is adjusted to pH 5 byaddition of citric acid. Then, 5 g of a 12.5% citric acid gel,comprising the dye of formula (13) of example 48 according to thepresent application, is applied on the hair and combed, so that the hairhas a pH of 7. After 15 minutes the hair is washed with water, rinsedand dried. The strand has been dyed in an intensive red shade, which hasa good wash and light fastness.

Example 45

[0853] A strand of bleached human hair is dyed with 10 g of acomposition having a pH of 9.8, which is obtained by mixing 5g of 6%hydrogen peroxide solution and 5 g of a composition A given in example51. After 15 minutes, the pH of the hair is adjusted to pH 5 by additionof citric acid. Then, 5 g of a 12.5% citric acid gel, comprising the dyeof formula (11) of example 46 according to the present application, isapplied on the hair and combed, so that the hair has a pH of 7. After 15minutes the hair is washed with water, rinsed and dried. The strand hasbeen dyed in an intensive red shade, which has a good wash and lightfastness.

Example 46

[0854] 26 g of 86% by weight of a compound of the following formula (10)

[0855] is added with stirring under nitrogen at 293 K to a solution of26 g of N,N-2,2-tetramethyl-1,3-propanediamine in 45 gdimethylformamide, whereby a viscose mixture is obtained. Then, thetemperature is raised to 355 K, and stirred 3 hour at this temperature.Then, 25 g of a compound of formula (10) is added to the reactionmixture, and the reaction mixture is stirred 25 hour at this temperatureunder nitrogen atmosphere. Afterwards, 170 g dimethyl-formamide is addedin 1.5 hours by a constant rate, while the temperature adjusted to 333K. During further stirring for 4 hours, the temperature is decreased to295 K. Then the reaction mass is filtered. The filter residue is washedwith 45 ml of dimethylformamide and then mixed with 300 ml water. Themixture is stirred for 3 hours at 343 K. Then, the temperature isdecreased to 295 K and the mixture filtered. Then, the filter residue iswashed with 100 ml of 3% sodium salt solution, filtered and dried invacuum to obtain 68 g of product with the following formula (11)

Example 47

[0856] 24 g of 2,2-dimethyl-1,3-propanediamine is added at 293 K, undernitrogen atmosphere, with stirring to 100 g isopropanol and 62 g of 85%by weight of a compound of the following formula (10), as given inexample 36. Then the temperature is raised then to 333 K, and viscosityof the reaction mixture decreases. The reaction mixture is stirred 28hour at this temperature. Then, the reaction mass is stirred for 4hours, while the temperature is decreased to 295 K. The reaction mass isfiltered, and the filter residue is washed with 45 ml of isopropanol andagain filtered. Then, 300 ml water is added to the humid filter residueand the mixture stirred for 3 hours at 353 K. Then, the temperature isdecreased to 295 K and the mixture filtered. Then, the filter residue iswashed with 100 ml water, filtered and dried in vacuum to obtain 57.6 gof product with the following formula (12)

Example 48

[0857] 21.4 g of 2,2-dimethyl-1,3-propanolamine is added at 293 K, undernitrogen atmosphere, with stirring to 100 g isopropanol, 4 g1,4-diazabicyclo[2.2.2]octan and 52 g of 85% by weight of a compound ofthe following formula (18)

[0858] Then the temperature is raised then to 333 K, and viscosity ofthe reaction mixture decreases. The reaction mixture is stirred at thistemperature during 5 hours. Then, the reaction mass is stirred for 4hours, while the temperature is decreased to 295 K. The reaction mass isfiltered and the filter residue is washed with 45 ml of isopropanol andagain filtered. Then, 300 ml water is added to the humid filter residueand the mixture stirred for 3 hours at 353 K. Then, the temperature isdecreased to 295 K and the mixture filtered. Then, the filter residue iswashed with 100 ml water, filtered and dried in vacuum to obtain 46 g ofproduct with the following formula (13)

Example 49

[0859] 1 g sodium methoxide is added under nitrogen atmosphere, at 293K, to a stirred mixture of 10.2 g of 2,2-dimethyl-1,3-propanediamine,100 g isopropanol, and 62 g of 85% by weight of a compound of formula(10) as given in example 36. Then, the temperature is raised then to 333K. The reaction mixture is stirred 28 hour at this temperature undernitrogen atmosphere. Then, he reaction mass is stirred for 4 hours,while the temperature is decreased to 295 K. The reaction mass isfiltered and the filter residue is washed with 45 ml of isopropanol andagain filtered. Then, 300 ml water is added to the humid filter residueand the mixture stirred for 3 hours at 353 K. Then, the temperature isdecreased to 295 K and the mixture filtered. Then, the filter residue iswashed with 100 ml water, filtered and dried in vacuum to obtain 37.6 gof product with the following formula (14)

Example 50

[0860] 16 g triethylamineis added under nitrogen atmosphere, duringstirring at 293 K, to a mixture of 10.2 g of2,2-dimethyl-1,3-propanediamine, 100 g methanol, and 55 g of a compoundof the following formula (13) as given in example 38, whereby a viscosemixture is obtained. Then the temperature is raised then to 335 K, andviscosity of the reaction mixture decreases. The reaction mixture isstirred 10 hour at this temperature under nitrogen atmosphere. Then, thereaction mass is stirred for 4 hours, while the temperature is decreasedto 295 K. The reaction mass is filtered, and the filter residue iswashed with 45 ml of methanol and again filtered. Then, 300 ml water isadded to the humid filter residue and the mixture stirred for 3 hours at353 K. Then, the temperature is decreased to 295 K and the mixturefiltered. Then, the filter residue is washed with 100 ml water, filteredand dried in vacuum to obtain 47.6 g of product with the followingformula (15)

Example 51

[0861] 37.6 g of compound of formula (14) of example 39 is added, undernitrogen atmosphere, at 293 K, to a stirred mixture of 16 g potassiumacetate (water free) and 400 g isopropanol. Then, the temperature israised then to 333 K, and viscosity of the reaction mixture decreases.The reaction mixture is stirred 2 hour at this temperature undernitrogen atmosphere. Then, the reaction mass is stirred for 4 hours,while the temperature is decreased to 293 K. The reaction mass isfiltered and the filter residue is washed with 45 ml of isopropanol andagain filtered. Then, the filter residue is washed with 10 mlisopropanol, filtered and dried in vacuum to obtain 30 g of product withthe following formula (16)

Example 52

[0862] 16 g 1,4-diazabicyclo[2.2.2]octan is added, under nitrogenatmosphere, at 293 K, to a stirred mixture of 150 g isopropanol, 23 g of1-amino-2,2-dimethyl-propane and 55 g of a compound of the followingformula (13) as given in example 38. Then, the temperature is raisedthen to 335 K, and viscosity of the reaction mixture decreases. Thereaction mixture is stirred 3 hour at this temperature under nitrogenatmosphere. Then, the reaction mass is stirred for 4 hours, while thetemperature is decreased to 295 K. The reaction mass is filtered and thefilter residue is washed with 45 ml of isopropanol and again filtered.Then, 300 ml water is added to the humid filter residue and the mixturestirred for 3 hours at 353 K. Then, the temperature is decreased to 295K and the mixture filtered. Then, the filter residue is washed with 100ml water, filtered and dried in vacuum to obtain 57 of product with thefollowing formula (17)

Example 53

[0863] 12.4 g 4-Fluoroanilin is added to a stirred solution of 25 mlwater and 25 ml of 32% hydrochloric acid at 295 K. Then, the reactionmixture is cooled to 273 K and 19 ml 36% sodium nitrite solution isdropped at such a rate that the temperature of the mixture is maintainedin the range of 273 to 276 K. After the addition of the sodium nitritesolution, the mixture is stirred for one hour. If no excess of nitriteis detected during one hour (detection by using a potassium iodidepaper), further amounts of sodium nitrite solution is added. After thisone hour the remaining excess of nitrite is destroyed with sulfamicacid. Then, the obtained diazo solution is dropped to a 273 K coldsolution of 7.4 g imidazole in 30 ml water, whereby the pH of thesolution is maintained in the range of pH 10 to 11 by adding 36% sodiumhydroxide solution. After completing the diazo addition, the obtainedsuspension is warmed up to 295 K, the pH is adjusted to 10.5 with 36%sodium hydroxide solution. After one hour stirring at this pH andtemperature, the suspension is filtrated and then washed twice with 50ml water to obtain 55 g of the humid product

[0864] Introduce into a reaction vessel 500 ml water, add the filtercakefrom the previouse step and suspend by stirring. Start the addition ofdimethylsulphate and parallel that of sodium Hydroxide, maintaining thepH at 10-10.3 and the temperature at 25-30° C. Add the amount of 0.3mole of dimethylsulphate in ca. 5 hours. Hold for one more hour, tofinish the hydrolysis of excess of dimethylsulphate. Controle thedisappearance of DMS. Then add 100 g of sodium chloride and 50 g ofpotassium chloride, cool to 0° C. After 16 hours the product isseparated by filtration and washed with a cold solution ofsodium/potassium chloride. Ca. 20 g cake with 0.07 mole product isobtained with the following formula (18)

Example 54

[0865] 12.4 g 4-Methoxyanilin is added to a stirred solution of 25 mlwater and 25 ml of 32% hydrochloric acid at 295 K. Then, the reactionmixture is cooled to 273 K and 19 ml 36% sodium nitrite solution isdropped at such a rate that the temperature of the mixture is maintainedin the range of 273 to 276 K. After the addition of the sodium nitritesolution, the mixture is stirred for one hour. If no excess of nitriteis detected during one hour (detection by using a potassium iodidepaper), further amounts of sodium iodide solution is added. After thisone hour the remaining excess of nitrite is destroyed with sulfamicacid. Then, the obtained diazo solution is dropped to a 273 K coldsolution of 7.4 g imidazole in 30 ml water, whereby the pH of thesolution is maintained in the range of pH 10 to 11 by adding 36% sodiumhydroxide solution. After completing the diazo addition, the obtainedsuspension is warmed up to 295 K, the pH is adjusted to 10.5 with 36%sodium hydroxide solution. After one hour stirring at this pH andtemperature, the suspension is filtrated and then washed twice with 50ml water to obtain 55 g of the humid product. This humid product isadded to 500 ml water, and suspend by stirring. Then, 0.3 moledimethylsulphate and sodium hydroxide is added in such a rate that a pHof pH 10-10.3 and a temperature in the range of 298 to 303 K aremaintained. After the addition, the mixture is stirred for one more hourto finish the hydrolysis of the excess of dimethylsulphate. Then, 100 gof sodium chloride and 50 g of potassium chloride, is added by 273 K.After 16 hours the product is separated by filtration and washed with acold solution of sodium/potassium chloride. About 20 g compound with0.07 mole product is obtained with the following formula (19)

1. Cationic dye of formula (1)

wherein R₁ and R₇ are each independently of the other hydrogen, hydroxyl; unsubstituted or substituted C₁-C₆alkyl, aryl radical or C₁-C₆alkoxy; or —NR₃R₄, wherein R₃ and R₄ are each independently of the other hydrogen, unsubstituted or substituted aryl radical or C₁-C₆alkyl, and R₂ is hydrogen, hydroxyl, unsubstituted or substituted C₁-C₆alkyl, aryl radical or C₁-C₆alkoxy, —NR₃R₄, or an organic radical of formula (2)

wherein R₅ is hydrogen, unsubstituted or substituted aryl radical or C₁-C₆alkyl, and X⁻ is an anion.
 2. Cationic dye according to claim 1, wherein R₁ and R₇ are each independently of the other hydrogen, unsubstituted C₁-C₆alkyl, —(C₁-C₆alkylen)—OH, —(C₁-C₆alkylen)—NR₃R₄ or —NR₃R₄, wherein R₃ and R₄ are each independently of the other hydrogen, unsubstituted C₁-C₆alkyl, and R₂ is hydrogen, hydroxyl, unsubstituted C₁-C₆alkyl, —(C₁-C₆alkylen)—OH, —(C₁-C₆alkylen)—NR₃R₄; or —NR₃R₄, or an organic radical of formula (2) as described in claim
 1. 3. Cationic dye according to claim 1, wherein R₁ and R₇ hydrogen.
 4. Cationic dye according to claim 1 of formula (3), (4), (5), (6) or (7)

wherein X⁻ is an anion.
 5. A process for the preparation of cationic dyes of formula (1) as defined above in claim 1, which comprises reacting a compound of formula (8)

wherein R₆ is C₁-C₆alkoxy or halide, and X⁻ is an anion, with an amine of formula (9)

wherein R₁, R₅ and R₇ are each independently of the other hydrogen, hydroxyl; unsubstituted or substituted C₁-C₆alkyl, aryl radical or C₁-C₆alkoxy; —NR₃R₄, wherein R₃ and R₄ are each independently of the other hydrogen, unsubstituted or substituted aryl radical or C₁-C₆alkyl; and X⁻ is an anion.
 6. A composition comprising at least a single cationic dye of formula (1) as defined above in claim 1, or prepared in accordance with a process according to claim
 5. 7. A composition according to claim 6 comprising in addition at least a single further direct dye and/or an oxidative agent.
 8. A composition according to claim 6 comprising in addition at least a single oxidative dye and/or; at least a single oxidative dye and an oxidative agent.
 9. Composition according to any one of claims 6, 7 or 8 in form of a shampoo, gel or emulsion.
 10. A method of dyeing organic material, especially human hair, that comprises bringing into contact with the organic material at least a single a cationic dye of formula (1) according to claims 1 to 4, or a composition according to claims 6 to 9, or a cationic dye as prepared according to claim 5, and, optionally, a further dye.
 11. A method according to claim 10 for dyeing or tinting human hair.
 12. A method for dyeing human hair or strands according to claims 10 or 11, that comprises contacting the hair with at least a single a cationic dye of formula (1) as defined in claim 1 and an oxidative agent and, optionally, a further direct dye.
 13. A method for dyeing human hair according to any of claims 10 to 12, that comprises contacting the hair with at least a single a cationic dye of formula (1) as defined in claim 1 and at least a single oxidative dye; or contacting the hair with a cationic dye of formula (1) as defined in claim 1 and at least a single oxidative dye and an oxidative agent. 